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Comparative Study on Sulfide and Oxide Electrolyte Interfaces with Cathodes in All-Solid-State Battery via First-Principles Calculations

Yukihiro Okuno*
Yukihiro Okuno
Research and Development Management Headquarters, FUJIFILM Corporation, 210 Nakanuma, Minamiashigara, Kanagawa 250-0193, Japan
*Email: [email protected] (Y.O.).
More by Yukihiro Okuno
,
Jun Haruyama
Jun Haruyama
Institute for Solid State Physics, The University of Tokyo, 5-1-5 Kashiwanoha, Kashiwa, Chiba 277-8581, Japan
More by Jun Haruyama
http://orcid.org/0000-0003-2310-4104
, and
Yoshitaka Tateyama*
Yoshitaka Tateyama
Center for Green Research on Energy and Environmental Materials (GREEN) and International Center for Materials Nanoarchitectonics (MANA), National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan
Elements Strategy Initiative for Catalysts & Batteries, Kyoto University, 1-30 Goryo-Ohara, Nishikyo-ku, Kyoto 615-8245, Japan
*Email: [email protected] (Y.T.).
More by Yoshitaka Tateyama
http://orcid.org/0000-0002-5532-6134

Cite this: ACS Appl. Energy Mater. 2020, 3, 11, 11061–11072

Publication Date (Web):October 28, 2020

https://doi.org/10.1021/acsaem.0c02033

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Abstract

The interfacial resistance between the solid electrolyte (SE) and the cathode of all-solid-state battery can crucially affect its performance. However, the microscopic mechanisms due to which this resistance occurs depend on the SE type and are still debatable. In this study, we performed a comparative analysis of the characteristics of sulfide electrolyte (Li₃PS₄) and oxide electrolyte (Li₃PO₄ and Li₇La₃Zr₂O₁₂) interfaces with a typical oxide cathode (LiCoO₂). We considered the Li vacancy formation associated with the Li chemical potential and the cation exchange related to the reaction layer formation, and used the density functional theory based on first-principles calculations. Compared to the case of sulfide SE interfaces, the oxide SE interfaces have fewer Li sites that have lower vacancy formation energy and are stable against the mutual cation exchange with the oxide cathode. These results indicate that the oxide electrolytes show less dynamical Li⁺ depletion upon initial charging and less formation of the reaction layer compared to those of sulfide electrolytes, which can be associated with the relatively low interfacial resistance observed experimentally. In addition to the material dependence, we also investigated the effect of the orientations of the SE and cathode at the interface. We demonstrated that the orientations strongly affect the ease of Li vacancy formation and mutual cation exchange. Interfaces of the buffer layer material of Li₄Ti₅O₁₂ with a Li₃PS₄ SE and the LiCoO₂ cathode were also evaluated. The results show that such oxide buffer layers suppress the Li vacancy formation, leading to less Li⁺ depletion. The present comparative analysis provides electronic and Li⁺ tendencies around the interfaces between the SE and the cathode, which will be useful for interface design in the future.

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1. Introduction

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There has been a rapid growth in the portable power source market owing to lithium-ion batteries (LIBs), which are presently attracting considerable attention for use in larger power sources such as electric vehicles and energy storage systems because of their high energy densities. (1−4) However, serious safety concerns exist around such future use because of their use of flammable organic solvent electrolytes. All-solid-state batteries (ASSBs), in which the organic liquid electrolyte is replaced with an inorganic solid electrolyte (SE), have many advantages such as safety, high energy density, and a long cycle life. (5,6) The development of Li-ion solid electrolytes has proceeded rapidly in recent years, and the conductivities of some systems have reached 25 mS cm^–1, approaching ∼100 mS cm^–1 of the typical liquid electrolyte. For example, new sulfide SEs such as Li₁₀GeP₂S₁₂ (7) and Li_9.54Si_1.74P_1.44S_11.7Cl_0.3 (8) show ion conductivities of σ > 10 mS cm^–1 at room temperature, and oxide SEs such as Li₇La₃Zr₂O₁₂ (9) (LLZO) and La_2/3–xLi_xTiO₃ (10) also typically show room-temperature ion conductivity of the order of 0.1 and 1 mS cm^–1, respectively.

Although various SE materials have already been synthesized, Li-ion ASSBs fabricated with these materials do not always show the expected performance because there are problems associated with the grain boundaries within the SE and the interface between the SE and the cathode. (11) For the latter, the interfacial resistance at the sulfide SE interfaces and the proposed solution by the interposition of an oxide buffer layer (e.g., Li₄Ti₅O₁₂ (LTO), (12) LiNbO₃, (13) and Li₂SiO₃ (14)) are well-known. (11) Several mechanisms were suggested as the origin of the interfacial resistance: (15) formation of a space-charge layer (SCL) of Li ions, (16,17) a structural disorder induced by interfacial chemical reactions involving mutual exchange of ions, (18−20) and the formation of secondary phases by the SE decomposition. (18−20) Although a buffer layer was introduced, the mutual ion exchange was still observed, and secondary phases were formed. In this respect, the SCL mechanism is still a reasonable candidate. (21−24) Compared to the sulfide SEs, the well-constructed oxide SEs showed low interfacial resistances for the cathode interfaces. Haruta et al. recently reported very low interfacial resistance for Li migration in a damage-less LiCoO₂ (LCO) cathode and Li₃PO_4–xN_x (LiPON) oxide electrolyte interface. (25) A low interface resistance of 7.6 Ω cm² was also reported for a system of LiNi_0.5Mn_1.5O₄ cathode and LiPON electrolyte (26) and for the interface of the LLZO electrolyte (27) and a Li metal anode. These results suggested the intrinsic absence of interfacial resistance for oxide SEs and that the structural disorder seems to be the more dominant origin of the interfacial resistance.

Thermodynamic calculations (28−33) and direct-interface calculations (21−24,34−36) within the density functional theory (DFT) framework were already performed computationally for the SE–cathode interfaces. The former studies showed a tendency for the sulfide SEs to have narrower electrochemical windows than those of oxide SEs, suggesting that interfacial reactions involving the appearance of secondary phases can occur thermodynamically more easily in the sulfide cases. The direct interface calculations demonstrated that at the sulfide SE–cathode interfaces specific mutual ion exchanges and the dynamical Li⁺ depletion with interfacial electron transfer can occur during operation. (21−24) Note that this dynamical Li⁺ depletion is different than the conventional static SCL formation mechanism. This suggests that in the initial stage of charging the Li⁺ depletion layer is dynamically generated from the Li sites that have a lower Li vacancy-formation energy near the interface along with electronic oxidation. (21,23,24) These findings can be related to the microscopic origin of the increase in interfacial resistance. In the direct approach, the buffer layer effect was also explained along with the above context. However, the comparison between the sulfide and oxide SEs and the investigation of interface orientation dependence are still lacking. In particular, the latter cannot be examined by the thermodynamic approach, but the surface/interface reactivity can be affected by the orientation.

We addressed this gap in existing research. In this study, we performed a comparative investigation between the sulfide Li₃PS₄ (LPS) and the oxide (Li₃PO₄ (LPO) and LLZO) SE interfaces with the LCO cathode materials in the framework of DFT direct-interface calculations. Using the interfacial structure search, we determined the probable interface structures and calculated the site-dependent Li vacancy-formation energy (E_f(V_{Li_j}) for the jth Li site), corresponding to the negative Li chemical potential (μ_{Li_j}), to discuss the possibility of dynamical Li⁺ depletion. We also calculated the mutual cation exchange energy at the interface of the SE and the cathode and examined cation diffusion across the interface. Following that, we investigated the interface orientation dependence of those quantities by calculating the Li vacancy-formation energy and the mutual cation exchange energy at LCO(110) and LCO(104) interfaces with LPS and LPO SEs. We constructed several slab models for each pair of cathode–SE interface and examined the physical quantities of the probable metastable structures because several metastable SE–cathode interfaces can appear under the actual battery operation. Furthermore, the buffer layer effect was investigated with LTO. We have already analyzed the buffer layer effect of LiNbO₃ (LNO) in our previous study (21) and suggested that electronic insulator oxide with d⁰ state of the transition metal is effective. To explore this effect, we selected LTO that has different crystal structure from LNO in this study. Taking all the results into account, together with the experimental observations, we evaluated the hypotheses proposed for the origin of interfacial resistance thus far and show differences in the interface properties between the sulfide and oxide SEs.

2. Calculation

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2.1. Interface Construction

In this study, we performed first-principles calculation analyses of five solid–solid interfaces: LCO/LPS, LCO/LPO, LCO/LLZO, LTO/LPS, and LCO/LTO. As model surface orientations for the interfaces, we selected LCO(104), LCO(110), LPS(010), LPO(010), LPO(001), LLZO(001), and LTO(111) because these are energetically probable. To prepare stable surface structures first, we chose the surface termination so as not to break the polyhedrons constructed by the transitional metal and anion atoms as much as possible within the stoichiometric surface slab. These slabs were approximately dipole-free as well. Next, we utilized a simpler version of the interface structure search scheme with the pristine surfaces in this study, although a comprehensive structure search technique for heterogeneous solid–solid interfaces was developed in a recent study. (24) In the construction of the supercell, the surface slab of LCO or LTO was set first, and the second material (SE) slab was put on it. To determine energetically stable structures, we explored several rigid lateral shifts of the second slab followed by local structure optimization. There was vacuum in the region surrounding the slabs (up to 1.5 nm) so that we can focus on the selected interface. We constructed several interface structures by randomly moving one side of the slab model in lateral directions for each solid–solid interface structure and calculated statistics of physical quantities such as Li vacancy-formation energies and cation exchange energies. Calculating the statistics of the physical properties is important to obtain reliable results. We believe that the various solid–solid interface structures obtained here will be realized in real ASSBs. The interface slab models were sampled, and the energy difference between each calculated structure and the most stable structure was evaluated; the structure with the energy difference of 1 order of magnitude higher than the others was excluded from further investigation.

The choices of the orientations were made with the following considerations. The (110) and (104) surfaces were chosen for LCO. Although the larger stability of the (104)-oriented LCO surface was suggested, (37) the (110) surface still exists in the LCO particles and is one of the theoretically well-studied LCO surfaces. (38−40) As a sulfide SE example, we adopted β-Li₃PS₄ (LPS) that shows high Li-ion conductivity (1.64 × 10^–4 S cm^–1 at room temperature). (41) The LPS (010) surface was selected because the Li⁺ conduction path in LPS is in the b direction. (42) γ-Li₃PO₄ (LPO) was selected as a model oxide electrolyte. Crystalline γ-Li₃PO₄ has an orthorhombic Pnma (43) structure, and in particular, LiPON (44,45) electrolyte materials are developed based on LPO. The (010)- and (001)-oriented LPO surfaces were selected in this work because b and c directions are Li⁺ conduction paths in LPO. (46,47) Considering the rather low elastic modulus of LPS, the LPS lattice constants are adjusted to that of LCO for the lattice mismatch at the LCO/LPS interface in the construction of the interface slab models. On the LPO surface, to keep the structure of the PO₄ tetrahedron at the interface, the outermost interface layer is composed of Li ions.

We also investigated LLZO as another oxide SE. LLZO has a garnet-type crystal structure with a relatively higher Li⁺ conductivity than the other oxide electrolytes. (9,48) In the cubic phase of the Ia3d space group with Li ions partially occupying 24 d tetrahedral and 48 g/96 h octahedral sites, LLZO shows a high Li-ion conductivity (43) of the order of 10 × 10^–4 S/cm². We selected the (001)-oriented surface of the cubic LLZO phase for the interfaces. On the Li sites of the Ia3d cubic phase, 7/9 of 24 d and 96 h sites of Li in the LLZO crystal are occupied. According to the previous calculations, (48) we introduced the vacancy in 50% and 40% of the 96 h and 24 d sites, respectively. (49,50) On the outermost surface of the LLZO slab, few LaO₈ dodecahedrons were broken, while the ZnO₆ octahedron structures were maintained.

For the oxide buffer layer, we selected Li₄Ti₅O₁₂ (LTO) (12) in this study. The LTO compound has a spinel structure with space group Fd3m (51) in which the 8 a positions are occupied by Li ions and 16 d positions are shared between Li and Ti in a ratio of 1:5. We treated the LTO (111)-oriented surface, where the Li ions can migrate through. (52) To maintain the TiO₆ octahedron structures, the outermost surfaces were composed of Li ions (8 a sites) on the TiO layers. The Li-terminated surface has the sequence of the (111) atomic-layer stacking similar to the bulk, implying that the Li-terminated (111)-oriented surface is stable for LTO. For the lattice constants parallel to the interface, the average of the two lattices is considered for the slab models with LCO and the oxide materials.

The thickness of all slab models is around 1–2 nm, which is sufficiently thick to show the bulk character in the central region of each slab. We also introduced a vacuum region with about 1–1.5 nm width in the outside of the interface slab. Note that a supercell without a vacuum usually involves two interfaces, which are atomically different in most cases.

The selected surface structures are shown in Figure 1, where the VESTA package (53) is used for visualization. The optimized lattice constants of bulk crystals are provided in Table S1 of the Supporting Information. The detailed structures of the slab models are also provided in the Supporting Information.

Figure 1. Surfaces of (a) LiCoO₂ (LCO)-(104), (b) LCO-(110), (c) β-Li₃PS₄ (LPS)-(010), (d) γ-L₃PO₄ (LPO)-(001), (e) Li₇La₃Zr₂O₁₂ (LLZO)-(001), and (f) Li₄Ti₅O₁₂(LTO)-(111), examined in this work. Li, O, P, S, Co, La, Zr, and Ti are depicted as light green, red, purple, yellow, blue, brown, blue, and light blue spheres, respectively. CoO₆, PS₄, PO₄, ZrO₆, LaO₈, and TiO₆ complexes are represented by blue, green, gray, light green, brown, and light blue polyhedrons, respectively.

2.2. Computational Details

DFT calculations were performed by using Quantum Espresso code. (54) The Hubbard U (DFT+U) (55) method was utilized d-orbitals of transition metal and ultrasoft pseudopotentials (56) were used for the treatment of the core electrons of atoms. The PBE (57) exchange correlation functional was used, and for the +U augmented treatment of Co 3d orbitals, we set the Hubbard U values as 4.9 eV. (58) The cutoff energies of wave function and charge density were set as 40 and 320 Ry, respectively. With regard to the K-point mesh, we set 2 × 1 × 1 for LCO(110)/LPS(010) and LCO(110)/LPO(001), and for other interface models, we set only the Γ-point. We set the system to be neutral, and the occupation number was determined by the Gaussian smearing technique with a smearing parameter of 0.001 Ry. With regard to the spin polarization of Co on the LCO surface, the spin-polarized state is stable because of the missing Co–O bonds. (59) However, we have investigated the Li passivation of the LCO(110) with and without spin polarization and found that energy difference among the low-, intermediate-, and high-spin states are within 0.2 eV per Co atom. Thus, we limit the present discussion to the spin-unpolarized case. The calculation conditions for the LLZO and LTO interfaces are the same as those for LCO(110)/LPS(010) and LCO(110)/LPO(001). Spin nonpolarization is assumed for these interfaces. For Ti, Zr, and La, no U values were applied.

The Li vacancy-formation energy at the jth Li site, E_f(V_{Li_j}), is defined as (21)

(1)

where E_tot(V_{Li_j}) and E_tot are the total energies of the relaxed interface obtained by DFT+U calculations with and without Li vacancy at the jth site, respectively. E_Li is the chemical potential of the bcc Li metal. To compare the stabilities of many Li sites in several interface systems, we adopted E_Li of Li metal as a common reference energy in this study. E_f(V_{Li_j}) indicates the energy required for the reaction Li_nX → Li_n–1X + Li(s) (n = integer and X = the rest moiety after Li vacancy formation at the jth site), which corresponds to the voltage with respect to the reference redox couple of Li/Li⁺. This is the negative chemical potential of Li with respect to Li metal, μ_{Li_j}. A lower E_f(V_{Li_j}) (a higher μ_{Li_j}) indicates that the Li⁺ at this site can be removed more easily. This scheme is valid when the electron can be extracted simultaneously; this means that the preceding chemical reaction can be divided into two electrochemical reactions: Li_nX → Li_n-1X + Li⁺(sol) + e^– and Li⁺(sol) + e^– → Li(s).

As a part of the reaction layer formation between the SE and cathode, we focused on the mutual cation exchange across the interface. The mutual ion exchange energy is defined as (22)

(2)

Here, E_tot is the total energy of the unexchanged pristine interface, and E_tot(A_j ↔ B_k) represents the total energy of a relaxed interface in which the jth A ion and kth B ion are mutually exchanged from the pristine interface. The negative exchange energy indicates that the mutual exchange is energetically favored. Note that the full evaluation of the exchange probability requires a consideration of the reaction kinetics.

3. Results and Discussion

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3.1. LCO/LPS Interface

First, we investigated the interface between the LCO cathode and a sulfide SE, LPS. Following the screening for the energy values, we sampled three and eight different structures for the LCO(104)/LPS(010) and LCO(110)/LPS(010) interfaces, respectively. The difference in energy per interface area between the most stable state and that with the highest energy among the selected states is 0.0053 and 0.0054 eV/Å², respectively, which is sufficiently low. In Figure 2, we show typical stable structures of LCO(104)/LPS(010) and LCO(110)/LPS(010) interfaces. For the LCO(104)/LPS(010) interface, almost half of the outermost Co cations in the LCO side attract S anions to form CoO₅S octahedrons, and the remaining outermost Co, not in close proximity to S anions, form CoO₅ quadrangular cones. Li ions in the LPS side are electrostatically attracted to O atoms in the LCO side and are located on the top position of O atoms. The estimated adhesion energy of the LCO(104)/LPS(010) interface is 0.025 eV/Å², where the definition of adhesion energy (60) of solid–solid interface is given in the Supporting Information. On the boundary of the LCO(110)/LPS(010), CoO₄ pseudotetrahedrals appear instead of typical CoO₆ octahedrons, and CoO₄S pentahedrons are also partly formed by attracting a S anion to a Co cation in the boundary region, as reported in a previous study. (21) Li ions in the LPS side of the interface interact with O atom in the LCO side and are located at the bridge positions with the O atoms. In summary, although the interface consists of the same substances as the cathode and electrolyte, the atomic structures formed at the interface are different if the crystal orientations are different.

Figure 2. Calculated interface structures with the lowest energies of (a) LCO(104)/LPS(010) and (b) LCO(110)/LPS(010). The insets show the detailed atomic structures at the interface. CoO₆ and PS₄ complexes are represented by blue and green polyhedrons.

Figure 3 shows the calculated partial density of states (PDOS) of the LCO(104)/LPS(010) interface. This PDOS is obtained from the most stable interface structures, whereas the PDOS features are common to the eight sampled structures. The result denotes that the valence band maximum (VBM) and the conduction band minimum (CBM) are composed of the orbitals originating from the LCO. In particular, the CBM is observed to be an in-gap state, consisting of the Co3d orbitals of CoO₅ quadrangular cones at the interface. The detailed PDOS of the first layer of LCO facing the LPS is shown in Figure S2.

Figure 3. PDOS of the calculated lowest energy interface of LCO(104)/LPS(010). Red line: total DOS; green line: LCO atoms; blue line: LPS atoms; brown line: LCO atoms facing the vacuum; light blue line: the first LCO layer facing the LPS slab. We set zero reference energy as the center of the band gap. LCO vac and LCO 1st correspond to the LCO layer facing the vacuum and the interface with LPS, respectively.

Next, we estimated the Li vacancy-formation energies at the LCO/LPS interface. Figure 4 shows the distribution of Li vacancy-formation energies. The Li sites were selected from each interfacial Li layer in the perpendicular direction of the cathode–SE interface. In Figure S3 and Table S3, we summarize E_f(V_{Li_j}) of the most stable and the highest energy structures of LCO(110)/LPS(010) interfaces we calculated.

Figure 4. Distributions of Li sites classified with the Li vacancy-formation energies at the (a) LCO(104)/LPS(010) and (b) both LCO/LPS interfaces, respectively. The vacancy-formation energies of 65 Li sites in 8 different interface structures (23 sites in three different interface structures) are calculated for LCO(104)/LPS(010) and (LCO(110)/LPS(010)). The distributions are normalized by the total number of calculated Li sites. The blue bars denote the distribution of all the calculated Li sites in the LCO/LPS and the red bars denote those of calculated Li sites located in the LPS region.

The distributions of Li sites classified by their vacancy-formation energies (Figure 4) show that sites with lower E_f(V_{Li_j}) (<2.0 eV) appear in both LCO(104)/LPS(010) and LCO(110)/LPS(010) interfaces. The sites with such low E_f(V_{Li_j}) are concentrated in the LPS side of the interfaces. In particular, we found that mobile Li sites in the original β-Li₃PS₄ crystal have a tendency to have low E_f(V_{Li_j}). The Li ions at these sites can be removed, together with oxidation of the materials, at the undervoltage condition upon the initial charging and lead to dynamical Li⁺ depletion in the interfacial LPS side. Such sites appear more frequently in the less stable LCO(110)/LPS(010) interfaces than in LCO(104)/LPS(010) interfaces, thereby reflecting the interface stability. As the dynamical Li⁺ depletion can be a major origin of the interfacial resistance, the LCO(110) interfaces have a higher resistance than that of the LCO(104). The details of the structure dependence of the Li vacancy-formation energies in LCO/LPS interfaces are discussed in Figure S3 and Table S3.

We also discuss the mutual cation exchange energies between the LCO(104)/LPS(010) and LCO(110)/LPS(010) interfaces. We previously calculated these energies in LCO(110)/LPS(010), (22) where the exchange between Co and P in the LCO/LPS interface was highly exothermic and energetically preferable to the unmixing pristine case. In Figure 5, we show the typical structure with the site assignments around the LCO(104)/LPS(010) interface and their corresponding cation exchange energies. We selected the Co and P atoms in the first and second layers from the LCO/LPS boundary. Co1, Co2, and Co3 form CoO₅S octahedrons, CoO₅ quadrangular cone, and CoO₆ octahedrons, respectively.

Figure 5. (a) Representative LCO(104)/LPS(010) interface structure with the site labels and the mutual cation exchange energies for (b) Co ↔ P and (c) Co ↔ Li.

As in the case of LCO(110)/LPS(010), the LCO(104)/LPS(010) interfaces show that the Co ↔ P exchange reaction is exothermic for the Co ↔ P1 (P cations in the first layer from the LCO/LPS boundary) case. However, the mixing reaction energies are around −0.7 to −1.2 eV, which are smaller than the energy of the LCO(110)/LPS(010) case (around −2 eV). (22) For the second-layer P cations, the exchange energies are almost endothermic, except for Co2 ↔ P2 in the LCO(104)/LPS(010) case. The results are in contrast to the LCO(110)/LPS(010) case. These results suggest that mutual cation exchange reactions are less likely to occur at the LCO(104) interface compared to the LCO(110). The reduced preference of Co ↔ P at the LCO(104)/LPS(010) interfaces is also confirmed in a recent study with an efficient sampling technique for the interface structures. (24) With regard to the Co ↔ Li exchange energies, the mixing reactions are about 2–3 eV endothermic even for the first layer of Li ions from the LCO/LPS boundary. Consequently, the Co cations cannot migrate to the neighboring Li sites. In this way, it was found that the mutual cation exchange energy depends on the interface orientation as in the Li vacancy-formation energy near the LCO/LPS boundary. In Figure S4, we also show the structure dependence of the mutual Co ↔ P exchange energy. The Co ↔ P exchange reaction is more likely to occur in structures with higher energy than in the most stable ones.

The mutual cation exchange can facilitate the generation of sites with low E_f(V_{Li_j}). In Table S4, we show the Li vacancy-formation energies for the LCO(104)/LPS(010) interface where we set Co ↔ P mixing in the first layer at the LCO/LPS interface as shown in Figure S5. The Co ↔ P mixing around the LCO/LPS boundary induces the generation of sites with lower E_f(V_{Li_j}), which may be related to the in-gap states appearing on the LCO interface as shown in PDOS (Figure S6). The Co ↔ P mixing increases the in-gap states composed of Co d-orbitals around the Fermi level, which lowers the electron transfer energy from LPS to LCO accompanied by the generation of a Li vacancy in the LPS side, and consequently, E_f(V_{Li_j}) in the LPS side decreases. As a result, the cation mixing introduces the Li⁺ depletion phase and becomes the origin of the high-resistance phase at the LCO/LPS interface. Note that in the high-energy interface the mutual Co ↔ P exchange is more likely to occur than in the stable interface state. Therefore, if the many interface structures between the cathode and SE are high-energy metastable states, the mutual cation exchange will proceed further. Note that the thermodynamic calculations (30) suggest LPS decomposition to P₂S₇, Co(PO₃)₂, Co₂S, and so on, in contact with LCO. Here we emphasize that the mutual cation exchange examined here is regarded as the initial stages of such chemical reactions toward the thermodynamically stable phases at the interface.

3.2. LCO/LPO Interface

We also investigated the characteristics of the oxide SE case to compare with the sulfide SE by focusing on γ-Li₃PO₄. For the LCO (104) surface, we prepared (010)- and (001)-oriented LPO surfaces, considering probable Li⁺ transport pathways. We considered five and four different interface structure models for the LCO(104)/LPO(010) and LCO(104)/LPO(001) structures, respectively. The energy difference per interface area between the most stable and the highest energy states among the calculated slab models are within 0.023 and 0.104 eV/Å² for the LCO(104)/LPO(010) and LCO(104)/LPO(001) interfaces, respectively.

In Figure 6, we show the optimized structures of the most stable LCO/LPO interfaces. The ion positions near the boundary of the LCO/LPO interfaces are not so deviated compared to the LCO/LPS case. For both interfaces, more than half of the outermost Co atoms at the LCO surface formed CoO₆ octahedrons by sharing the O atoms in the PO₄ tetrahedrons in the LPO region. These newly formed CoO₆ octahedrons may be related to the rather smooth arrangement at the LCO/LPO interfaces. The adhesion energy of the LCO(104)/LPO(010) and LCO(104)/LPO(001) interfaces are 0.028 and 0.021 eV/Å², respectively.

Figure 6. Optimized interface structures of (a) LCO(104)/LPO(010) and (b) LCO(104)/LPO(001). The insets show the detailed atomic structures at the interface. CoO₆ and PO₄ complexes are represented by blue and gray polyhedrons.

We show the calculated PDOS of the representative LCO(104)/LPO(001) interface in Figure 7. As in the case of the sulfide SE, the VBM is composed of LCO orbitals, and the contribution of LPO to the valence band lies ∼1 eV lower than the VBM. The CBM consists of LCO components, and the in-gap state around 0.7 eV originated from Co’s d-orbital at the interfacial LCO.

Figure 7. PDOS of the optimized interfaces of LCO(104)/LPO(001). Red line: total DOS; green line: PDOS from LCO atoms; blue line: PDOS from LPO atoms; brown line: PDOS from LCO atoms facing the vacuum; light blue line: PDOS from first LCO layer facing the LPO slab. We set zero reference energy as the band gap center.

We then evaluated the Li site distribution classified by the vacancy-formation energy around the LCO/LPO interfaces (Figure 8). The energy range is between 1.6 and 3.6 eV, which is more than 1 eV smaller than that in the bulk region of LPO (about 5.0 eV). E_f(V_{Li_j}) in the LPO side is about 3.6 eV at the maximum, and it reflects the band offset between the LCO and LPO interfaces. In bulk LPO, the electron extracted with the Li vacancy formation is located at the VBM of LPO, while in the LCO/LPO interface, the electron is extracted from the LCO band as shown in Figure 7. Figure 8 shows that the percentage of sites with low E_f(V_{Li_j}) is low for the LCO/LPO interface compared to the LCO/LPS interface. Notably in the LCO(104)/LPO(010) interface (Figure 8a), even in the highest energy state in our sampling models, there is no Li site with low E_f(V_{Li_j}) less than 2.0 eV. With regard to the structural dependence of E_f(V_{Li_j}) for LCO(104)/LPO(001) (Figure 8b), we found that sites with low E_f(V_{Li_j}) are observed in high-energy interface structures. This may be related to the fact that the low interfacial resistance of the LCO/LPO interface requires a damage-less LCO cathode and a Li₃PO_4–xN_x (LiPON) oxide electrolyte interface. (25) Detailed analyses of E_f(V_{Li_j}) are provided in Figure S9 and Table S6.

Figure 8. Distributions of Li sites divided by their Li vacancy-formation energies at the (a) LCO(104)/LPO(010) and (b) LCO(104))/LPO(001) interfaces. The vacancy-formation energies of 28 Li sites in four different interface structures and 36 sites in five different interface structures are calculated for LCO(104)/LPO(010) and LCO(104)/LPO(001), respectively. The distributions are normalized by the total number of calculated Li sites. The blue bar graphs denote the distribution of all the calculated Li sites in LCO/LPO, and the red bar graphs denote those of the calculated Li sites located in the LPO region.

In Figure 9a, we show a schematic picture of the LCO(104)/LPO(001) interface with the Li and cation sites where mutual cation exchange energies were calculated. With regard to the cation sites where the mutual ion exchanges were evaluated, Co1 and Co3 are the outermost surface-Co ions on the LCO surface, and Co2 is a second-layer Co ion from the LCO/LPO boundary. We selected the Li and P atoms in the first and second layers of LPO from the LCO/LPO boundary.

Figure 9. (a) Schematic picture of the optimized LCO(104)/LPO(001) interface with the sites where we calculated mutual cation exchange energy. (b) Co ↔ P and (c) Co ↔ Li cation exchange energies corresponding to sites denoted in (a).

From Figure 9b,c, we see that the reaction energies of cation exchange between LCO and LPO are highly endothermic. Unlike the sulfide LPS case, the exchange energies of Co ↔ P and Co ↔ Li are over 3 eV, and the LPO surface is inert to reactions with the LCO surface. This result suggests that unlike in case of LPS, Co diffusion is less likely to occur on the LPO phase. Here, we point out that the thermodynamics consideration can also show the inertness of interface reactivity between LCO and LPO. In Figure S10, we also show the vacancy-formation energies of Li sites in the LCO(110)/LPO(010) interface. Compared with the LCO(104)/LCO(010) case, the percentage of sites with low E_f(V_{Li_j}) increases, and it may be related to the strong chemical activity of the LCO(110) surface compared to that of LCO(104). However, when compared to the sulfide SE, we can conclude that the number of occurrences of Li sites with low E_f(V_{Li_j}) decreases at LCO/LPO. This result suggests the absence of a high-resistance phase at the LCO/LPO interface is related to the LCO/LiPON interface, in which the high-resistance phase is absent, as demonstrated by Haruta et al. (25) LPO has a larger bandgap and a lower valence-band maximum than that of LPS. The large band offset of the valence band between the cathode and SE is an obstacle for electron transfer from SE to the cathode when Li⁺ ions are removed from the SE side, leading to the suppression of dynamical Li⁺ depletion layer generation, which can be associated with the suppression of interfacial resistance. (21,23)

3.3. LCO/LLZO Interface

We investigated the interface with another oxide electrolyte, LLZO, which is unique in that it is a fast Li-ion conductor among the oxide electrolytes. For the surface of LLZO with the LCO (104), we chose the (001) surface maintaining the structure of the ZrO₆ octahedron in LLZO. We considered four different interface structure models for the LCO(104)/LLZO(001) interface. The energy difference per interface area between the most stable and the highest energy states in the calculated models is 0.038 eV/Å² for the LCO(104)/LLZO(001) interface.

In Figure 10, we show typical stable structures of LCO(104)/LLZO(001). At the LCO–LLZO boundary, more than half of the outermost Co atoms form CoO₆ octahedrons by sharing O atoms in the ZrO₆ tetrahedrons in the LLZO region, as shown in the insets of Figure 10.

Figure 10. Optimized interface structures of LCO(104)/LLZO(001). The insets show the detailed atomic structures at the interface. CoO₆, ZrO₆, and LaO₈ complexes are represented by dark blue, light green, and brown polyhedrons.

Figure 11 shows the calculated PDOS of the LCO(104)/LLZO(001) interface. Both the VBM and CBM are composed of LCO orbitals as in the case of the LCO/LPO interface. The CBM is an in-gap state which consists of Co 3d orbitals of CoO₅ quadrangular cones at the interface, and it is one of the common properties of LCO(104) and the oxide SE interfaces that we investigated. The contribution of LLZO orbitals to the conduction band is at least 1 eV above the CBM, and the band offset of LCO/LLZO on the conduction band is considerably large. The top of the valence band is also composed of LCO orbitals, and the contribution of LLZO to the valence band appears just around 0.2 eV lower than the VBM, leading to a smaller band offset. We also show the PDOS of LCO(104)/LLZO(001), divided to show each ion contribution in Figure S14. The VBM of the LLZO side mainly consists of O orbitals and hybridization between the O orbital and that of Zr (or La) in the LLZO slab and is not as strong as in the case of the oxygen and Co in the LCO slab.

Figure 11. PDOS of the optimized interfaces of LCO(104)/LLZO(001). Red line: total DOS; green line: LCO atoms; blue line: LLZO atoms; violet line: LCO atoms facing the vacuum; light blue line: the first LCO layer facing the LLZO slab. We set zero reference energy as the center of the band gap.

Next, we examined the distribution of E_f(V_{Li_j}) around the LCO(104)/LLZO(001) interface, which is shown in Figure 12. In the sampling of LCO(104)/LLZO(001) interfaces, we excluded the interface structures that became metallic due to the in-gap state originated from the LLZO surface. The metallic interface structures had energies per interface area that were 2 orders of magnitude larger with respect to the most stable structure than those of the other insulating interface structures. The percentage of Li sites with low E_f(V_{Li_j}) decreases for the LCO(104)/LLZO(001) interface compared to the LCO/LPS interface. However, the number of Li sites with low E_f(V_{Li_j}) increases compared to that of the LCO/LPO case. This property is related to the small offset in the valence band of the LCO(104)/LLZO(001) case, where the electron transfer from SE to the cathode easily occurs compared to the LCO/LPO interface. The sites with low E_f(V_{Li_j}) appear in the interface structures with rather high energies. In the LCO(104)/LLZO(001) interface, some LaO₈ complexes in LLZO are broken at the interface and deform the atomic structure. As a result, a high-energy interface structure is formed, which can be an origin of Li⁺ transport resistance. The details of E_f(V_{Li_j}) are provided in Figure S15 and Table S9.

Figure 12. Distributions of the Li sites classified by their Li vacancy-formation energies at the LCO(104)/LLZO(001) interface. The vacancy-formation energies of 36 Li sites in four different interface structures are calculated. The distributions are normalized by the total number of calculated Li sites. The blue bar graphs denote the distribution of all the calculated Li sites in LCO/LLZO, and the red bar graphs denote those of the calculated Li sites located in the LLZO region.

The reactivity of the LCO(104)/LLZO(001) surface was examined by estimating mutual cation exchange energies among Co atoms in the LCO phase and those of Zr, La, and Li atoms in the LPO phase. In Figure 13, we show the mutual cation exchange energies of Co ↔ Zr and Co ↔ La. The mutual exchange energy of Co ↔ Li is provided in Figure S16, and we only briefly describe the results. As shown in Figure 13, both cation exchange energies are endothermic. The Co ↔ La exchange energy is endothermic by over 1 eV, and in particular, the exchange of the Co atom in the second layer from the boundary of LCO/LLZO is endothermic by more than 3.0 eV and is less likely to occur. The endothermic reaction energies of the Co ↔ Zr exchange are 0.7–1 eV and are smaller than that of Co ↔ La. This suggests that the ion radii and oxygen ligand environment of Co atoms are more similar to those of Zr atoms than those of La atom. The Co ↔ Li exchange energies are 2–3 eV, and Li sites are present in the first and second layers from the LCO/LLZO boundary. Overall, the cation exchange of the LCO/LLZO interface is unlikely to occur. However, if we compare the LCO/LPO surface, where all the cation exchange reaction energies are endothermic by over 3 eV, the reaction layer formation related to the cation exchange at the LCO/LLZO interface seems easier than at the LCO/LPO interface.

Figure 13. (a) Structure of the LCO(104)/LLZO(001) interface (upper panel) and its corresponding (b) Co ↔ Zr and (c) Co ↔ La mutual cation exchange reaction energies (lower panel). The positive values of exchange energies indicate endothermic reactions.

3.4. Interface of Oxide Buffer Layer LTO

Finally, we analyzed the interface properties of the oxide buffer layer, which is often introduced between the oxide cathode and sulfide SE to reduce the interfacial resistance. We have previously investigated the effect of the oxide buffer layer LiNbO₃ between LCO and LPS and found that the introduction suppresses the appearance of sites with low E_f(V_{Li_j}) in the LPS side and the interfacial electron transfer leading to the LPS oxidation. In this study, to understand the common features of the buffer later, we examined Li₄Ti₅O₁₂ (LTO), a representative oxide used as a buffer layer.

We first discuss a low-energy structure of the LTO(111)/LPS(010) interface (Figure 14), where no TiO₆ octahedron is broken at the boundary to LPS, and the interface bond with S atoms of LPS is not formed, unlike in the case of LCO/LPS. Thus, the interface preserves the atomic structure of the bulk crystal. It is also found at the LTO/LPS interface that the Li atoms of LPS closest to the LTO surface are located on the bridge position between the O atoms of the LTO surface. The PDOS of the LTO/LPS interface is shown in Figure 15. In contrast to the LCO/LPS interface, there is no gap state around the interface. The CBM is composed of LTO and the LPS states are located 1 eV higher than the CBM, while the VBM consists of the LPS state and the states of LTO are lower than −1.5 eV with respect to the VBM. The adhesion energy between LTO and LPS is 0.019 eV/Å² and is smaller than those of the LCO/LPS interfaces.

Figure 14. Optimized interface structures of LTO(111)/LPS(010). The insets show the detailed atomic structures at the interface. TiO₆ and PS₄ complexes are represented by light blue and green polyhedrons.

Figure 15. PDOS of the optimized interfaces of LTO(111)/LPS(010). Red line: total DOS; gray line: LTO atoms; blue line: LPS atoms. We set zero reference energy as the center of the band gap.

We then examined the distribution of the Li vacancy-formation energies around the LTO(111)/LPS(010) interface, as shown in Figure 16. The values of E_f(V_{Li_j}) in the LTO phase are in the range of 3.0–4.0 eV, and these values are ∼1 eV smaller than the calculated value for the LTO bulk of around 5.0 eV. It reflects the valence band offset between the LTO and LPS. In the bulk LTO, the electron extracted with Li vacancy formation is located at the valence band top of LTO, while in the LTO/LPS interface, the electron is extracted from the LPS-originated band. With regard to the Li vacancy-formation energies in the LPS side, although the sites with E_f(V_{Li_j}) = 2.0–2.5 eV are generated, the distribution of the sites with E_f(V_{Li_j}) above 2.5 eV is widened compared to the that of LCO/LPS. In our sampling of E_f(V_{Li_j}), no site with E_f(V_{Li_j}) less than 2.0 eV was found. The electronic states and the vacancy-formation energies indicate that the dynamical Li⁺ depletion is suppressed by the LTO buffer later, which may lead to lower interfacial resistance.

Figure 16. Distributions of Li sites divided by their Li vacancy-formation energies at the LTO(111)/LPS(010) interface. The vacancy-formation energies of 31 Li sites in four different interface structures are calculated. The distributions are normalized by the total number of calculated Li sites. The blue bar graphs denote the distribution of all the calculated Li sites in LTO/LPS, and the red bar graphs denote those of calculated Li sites located in the LPS region.

At the LTO/LPS interface, we did not observe the stabilization of the interface structure by mutual cation exchange as observed in the LCO/LPS case, and both the Ti ↔ P and Ti ↔ Li cation exchange energies are over 1 eV endothermic. (The details are shown in Figures S19 and S20.) This result suggests that the effect of the LTO buffer layer is inert to the LPS surface. Therefore, the LTO buffer layer is effective from two viewpoints, suppressing the generation of Li sites with low E_f(V_{Li_j}) and suppressing the cation diffusion into the sulfide electrolyte.

Here, we comment on the other oxide buffer layer. We previously evaluated the values of E_f(V_{Li_j}) around the interface region between LiNbO₃ (LNO) and LPS and demonstrated that the vacancy formations energies have an average of around 3.0 eV and a minimum of 2.4 eV. (21) These are larger than those of the present LTO/LPS interfaces, implying that the LNO buffer layer is superior to LTO for decreasing the interfacial resistance.

To conclude, we briefly describe the calculation results of the LCO(104)/LTO(111) interface. The details of the calculation are shown in section S7 of the Supporting Information. The probability of appearance of sites with low E_f(V_{Li_j}) is very low at this interface. Sites with E_f(V_{Li_j}) below 2.5 eV did not appear. Therefore, the coating of LTO on the LCO surface do not produce the interfacial resistive phase between these two phases.

4. Summary

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We investigated the LCO/LPS, LCO/LPO, LCO/LLZO, and LCO/LTO/LPS interfaces by using first-principles calculations. Statistics of physical quantities such as Li vacancy-formation energies (E_f(V_{Li_j})) and mutual cation exchange energies were evaluated for several solid–solid interfaces with reasonable stabilities. Subsequently, the interfacial reactivities and ionic resistances were discussed based on the calculated quantities.

Compared to the sulfide SE, oxide SEs such as LPO and LLZO clearly show fewer sites with low E_f(V_{Li_j}) and are less reactive to the LCO surface. In the oxide SE, the large valence band offset at the cathode–SE interface suppresses the electron transfer from the electrolyte to the cathode; this causes a decrease in the number of sites with low E_f(V_{Li_j}). These results indicate that the appearance of interfacial disorder is suppressed in oxide SEs; this is consistent with the recent experimental results (25) of interfaces between LCO and LiPON. Although LiPON is amorphous, we believe that our calculated models of LCO/LPO capture the characteristics of actual LCO/LiPON, such as band offsets and atomic structure at the interface. Furthermore, when considering the LPO and LLZO oxide SEs, there is a difference in the tendency of the generation of sites with low E_f(V_{Li_j}). The observation can be mainly attributed to the difference in valence band offsets at the cathode and electrolyte. A smaller band offset in VBM in the LCO/LLZO interface compared to the LCO/LPO interface will allow easier electron transfer from the electrolyte; this results in SE oxidation and generates sites with low E_f(V_{Li_j}). Furthermore, the LLZO interface tends to become a high-energy structure because of the atomic disorder caused by broken complexes such as LaO₈ in LLZO. Therefore, a high-energy metastable state is likely to occur, which may induce dynamical Li⁺ depletion.

Different surface orientations of crystals at the boundary of the cathode and electrolyte were compared. Compared to the LCO(104) surface, the LCO(110) surface is more reactive to LPS and generates more sites with low E_f(V_{Li_j}) at the boundary with LPS. It suggests that the Li conductive resistivity at the cathode-SE interface depends on the crystal orientation of the surface and that the LCO(110) surface has a higher interface resistance than that of LCO(104). This tendency is also observed at the boundary of the LCO/LPO interface. Other than the orientation dependence of the LCO cathode material, the orientation of LPO to the LCO interface also affects the generation of sites with low E_f(V_{Li_j}). In addition, we show that high-energy interface structures show a tendency of increased number of sites with low E_f(V_{Li_j}).

On the buffer coating layer, we calculated LTO/LPS and LTO/LCO interface models. The LTO surface suppressed the low E_f(V_{Li_j}) of the sites and was inert to the LPS surface. The calculated results are consistent with the fact that LTO is an effective buffer layer oxide for sulfide SE. (12) The reason for the effectiveness of the buffer layer could be attributed to several factors, but in particular, the large valence band offset of the LTO/LPS interface could play an important role.

In this study, we limit the interfacial structures we dealt with to clean interfaces that are free from defects and reaction phase. For more realistic interface structure, a more efficient structure search method for interface region is needed. (23,24) Such a method will enable to examine more complicated interfaces such as Li₆PS₅Cl/Li₂S (61) and Li_3+xP_1–xSi_xO₄/LiFePO₄ interfaces (62) with large resistances recently investigated.

The results on the atomic scale of the interfaces between the cathode and electrolyte and the comparison between oxide and sulfide SE interfaces provide useful guidelines for designing stable cathode–electrolyte and buffer oxide–electrolyte interfaces, which is a crucial bottleneck in the development of ASSBs.

Supporting Information

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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsaem.0c02033.

Calculated bulk structures and vacancy formation energies of LCO, LPS, LPO, and LLZO; structure models, projected density of states, representative sampled structures, site-dependent vacancy formation energies, cation mixing energies, obtained in the calculations of the LCO(104)/LPS(010), LCO(110)/LPS(010), LCO(104)/LPO(001), LCO(104)/LPO(010), LCO(110)/LPO(010), LCO(104)/LLZO(001), LTO(111)/LPS(010), and LCO(104)/LTO(111) interfaces (PDF)

ae0c02033_si_001.pdf (4.28 MB)

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Author Information

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Corresponding Authors
- Yukihiro Okuno - Research and Development Management Headquarters, FUJIFILM Corporation, 210 Nakanuma, Minamiashigara, Kanagawa 250-0193, Japan; Email: [email protected]
- Yoshitaka Tateyama - Center for Green Research on Energy and Environmental Materials (GREEN) and International Center for Materials Nanoarchitectonics (MANA), National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan; Elements Strategy Initiative for Catalysts & Batteries, Kyoto University, 1-30 Goryo-Ohara, Nishikyo-ku, Kyoto 615-8245, Japan; http://orcid.org/0000-0002-5532-6134; Email: [email protected]
Author
- Jun Haruyama - Institute for Solid State Physics, The University of Tokyo, 5-1-5 Kashiwanoha, Kashiwa, Chiba 277-8581, Japan; http://orcid.org/0000-0003-2310-4104
Notes
The authors declare no competing financial interest.

Acknowledgments

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Y.O acknowledges the support of Mrs. M. Suzuki at FujiFilm Corporation. This work was supported in part by MEXT as “Program for Promoting Researches on the Supercomputer Fugaku (Fugaku Battery & Fuel Cell Project), Grant JPMXP1020200301, Elements Strategy Initiative, Grant JPMXP0112101003, and the Materials Processing Science project (“Materealize”), Grant JPMXP0219207397. The work was also supported by JSPS KAKENHI Grant JP19H05815. The calculations were performed on the K computer at the RIKEN AICS through the HPCI System Research Projects (project IDs: hp160081, hp170292, and hp190039).

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8
Kato, Y.; Hori, S.; Saito, T.; Suzuki, K.; Hirayama, M.; Mitsui, A.; Yonemura, M.; Iba, H.; Kanno, R. High-power all-solid-state batteries using sulfide superionic conductors. Nat. Energy 2016, 1, 16030, DOI: 10.1038/nenergy.2016.30
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8
High-power all-solid-state batteries using sulfide superionic conductors
Kato, Yuki; Hori, Satoshi; Saito, Toshiya; Suzuki, Kota; Hirayama, Masaaki; Mitsui, Akio; Yonemura, Masao; Iba, Hideki; Kanno, Ryoji
Nature Energy (2016), 1 (4), 16030CODEN: NEANFD; ISSN:2058-7546. (Nature Publishing Group)
Compared with Li-ion batteries with liq. electrolytes, all-solid-state batteries offer an attractive option owing to their potential in improving the safety and achieving both high power and high energy densities. Despite extensive research efforts, the development of all-solid-state batteries still falls short of expectation largely because of the lack of suitable candidate materials for the electrolyte required for practical applications. Here the authors report Li superionic conductors with an exceptionally high cond. (25 mS cm-1 for Li9.54Si1.74P1.44S11.7Cl0.3), as well as high stability ( ∼0 V vs. Li metal for Li9.6P3S12). A fabricated all-solid-state cell based on this Li conductor has very small internal resistance, esp. at 100 oC. The cell possesses high specific power that is superior to that of conventional cells with liq. electrolytes. Stable cycling with a high c.d. of 18 C (charging/discharging in just 3 min; where C is the C-rate) is also demonstrated.
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Murugan, R.; Thangadurai, V.; Weppner, W. Fast Lithium Ion Conduction in Garnet-Type Li₇La₃Zr₂O₁₂. Angew. Chem., Int. Ed. 2007, 46, 7778– 7781, DOI: 10.1002/anie.200701144
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9
Fast lithium ion conduction in garnet-type Li7La3Zr2O12
Murugan, Ramaswamy; Thangadurai, Venkataraman; Weppner, Werner
Angewandte Chemie, International Edition (2007), 46 (41), 7778-7781CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
Low activation energy and fast Li ion conduction were obsd. for the new compd., Li7La3Zr2O12. Relative to previously reported Li garnets, this solid electrolyte shows a larger cubic lattice const., higher Li ion concn., lower degree of chem. interaction between the Li+ and the other lattice constituents, and higher densification.
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Inaguma, Y.; Liquan, C.; Itoh, M.; Nakamura, T.; Uchida, T.; Ikuta, H.; Wakihara, M. High ionic conductivity in lithium lanthanum titanate. Solid State Commun. 1993, 86, 689– 693, DOI: 10.1016/0038-1098(93)90841-A
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10
High ionic conductivity in lithium lanthanum titanate
Inaguma, Yoshiyuki; Chen, Liquan; Itoh, Mitsuru; Nakamura, Tetsuro; Uchida, Takashi; Ikuta, Hiromasa; Wakihara, Masataka
Solid State Communications (1993), 86 (10), 689-93CODEN: SSCOA4; ISSN:0038-1098.
The polycryst. Li0.34(1)La0.51(1)TiO2.94(2) shows high ionic cond. >2 × 10-5 cm-1 (d.c. method) at room temp., which is compared with that of Li3.5V0.5Ge0.5O4. This compd. has cubic perovskite structure whose cell parameter is 3.8710(2) Å. By a.c. impedance anal., the equiv. circuit of the sample could be divided into 2 parts; bulk crystal and grain boundary. The ionic cond. of the bulk part is as high as 1 × 10-3 S cm-1 at room temp. Such a high cond. is considered to be attributed to the presence of a lot of equiv. sites for Li ion to occupy and freely move in this perovskite. This compd. is easy to react with Li metal and the electronic cond. has become much higher than before being in contact with Li. It can be explained that Ti ion was reduced by Li insertion into a vacant site and then an electron carrier was introduced.
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Takada, K.; Ohta, N.; Zhang, L.; Fukuda, K.; Sakaguchi, L.; Ma, R.; Osada, M.; Sasaki, T. Interfacial modification for high-power solid-state lithium batteries. Solid State Ionics 2008, 179, 1333– 1337, DOI: 10.1016/j.ssi.2008.02.017
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11
Interfacial modification for high-power solid-state lithium batteries
Takada, Kazunori; Ohta, Narumi; Zhang, Lianqi; Fukuda, Katsutoshi; Sakaguchi, Isao; Ma, Renzhi; Osada, Minoru; Sasaki, Takayoshi
Solid State Ionics (2008), 179 (27-32), 1333-1337CODEN: SSIOD3; ISSN:0167-2738. (Elsevier B.V.)
Interfaces between LiCoO2 and sulfide solid electrolytes were modified in order to enhance the high-rate capability of solid-state lithium batteries. Thin films of oxide solid electrolytes, Li4Ti5O12, LiNbO3, and LiTaO3, were interposed at the interfaces as buffer layers. Changes in the high-rate performance upon heat treatment revealed that the buffer layer should be formed at low temp. to avoid thermal diffusion of the elements. Buffer layers of LiNbO3 and LiTaO3 can be formed at low temp. for the interfacial modification, because they show high ionic conduction in their amorphous states, and so are more effective than Li4Ti5O12 for high-power densities.
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Ohta, N.; Takada, K.; Zhang, L.; Ma, R.; Osada, M.; Sasaki, T. Enhancement of the high-rate capability of solid-state lithium batteries by nanoscale interfacial modification. Adv. Mater. 2006, 18, 2226– 2229, DOI: 10.1002/adma.200502604
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12
Enhancement of the high-rate capability of solid-state lithium batteries by nanoscale interfacial modification
Ohta, Narumi; Takada, Kazunori; Zhang, Lianqi; Ma, Renzhi; Osada, Minoru; Sasaki, Takayoshi
Advanced Materials (Weinheim, Germany) (2006), 18 (17), 2226-2229CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)
The high-rate capability of solid-state rechargeable Li batteries with sulfide electrolytes improved when the LiCoO2 particles are spray-coated with Li4Ti5O12. The power densities of the solid-state battery with the coated LiCoO2 are comparable to those of com. Li-ion batteries.
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Ohta, N.; Takada, K.; Sakaguchi, I.; Zhang, L.; Ma, R.; Fukuda, K.; Osada, M.; Sasaki, T. LiNbO₃-coated LiCoO₂ as cathode material for all solid-state lithium secondary batteries. Electrochem. Commun. 2007, 9, 1486– 1490, DOI: 10.1016/j.elecom.2007.02.008
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13
LiNbO3-coated LiCoO2 as cathode material for all solid-state lithium secondary batteries
Ohta, Narumi; Takada, Kazunori; Sakaguchi, Isao; Zhang, Lianqi; Ma, Renzhi; Fukuda, Katsutoshi; Osada, Minoru; Sasaki, Takayoshi
Electrochemistry Communications (2007), 9 (7), 1486-1490CODEN: ECCMF9; ISSN:1388-2481. (Elsevier B.V.)
The enhancement of the high-rate capabilities for solid-state Li secondary batteries is reported. A nanometer thick LiNbO3 layer was interposed between LiCoO2 and the solid sulfide electrolyte as buffer layer. This decreased the interfacial resistance in the cathode and enhanced the high-rate capabilities of the batteries - this can enable design of Li secondary batteries free from safety issues.
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Sakuda, A.; Kitaura, H.; Hayashi, A.; Tadanaga, K.; Tatsumisago, M. Modification of Interface Between LiCoO₂ Electrode and Li₂S – P₂S₅ Solid Electrolyte Using Li₂O – SiO₂ Glassy Layers. J. Electrochem. Soc. 2009, 156, A27– A32, DOI: 10.1149/1.3005972
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14
Modification of Interface Between LiCoO2 Electrode and Li2S-P2S5 Solid Electrolyte Using Li2O-SiO2 Glassy Layers
Sakuda, Atsushi; Kitaura, Hirokazu; Hayashi, Akitoshi; Tadanaga, Kiyoharu; Tatsumisago, Masahiro
Journal of the Electrochemical Society (2009), 156 (1), A27-A32CODEN: JESOAN; ISSN:0013-4651. (Electrochemical Society)
Effects of modification of the electrode/electrolyte interface with Li2O-SiO2 thin films on impedance profiles and rate capabilities of all-solid-state In/80Li2S·20P2S5 glass ceramic/LiCoO2 cells were studied. Large resistance was obsd. at the LiCoO2-electrode/sulfide-electrolyte interface in all-solid-state cells. The interfacial resistance was decreased by 0.06% oxide coatings on LiCoO2; the effective coatings were a Li-ion conductive Li2SiO3 glassy film and an insulative SiO2 film. The Li2SiO3 coating film decreased the interfacial resistance more effectively when the coating amts. increased from 0.06 to 0.6% (film thickness was ∼10 nm). However, 0.6% of SiO2 coating exhibited higher interfacial resistance than non-coating because the thick SiO2 coating film acted as a high-resistance layer. Temp. dependence of the interfacial resistance suggests that the resistance decrease was achieved mainly by an increase of pre-exponential factor rather than by a decrease of activation energy for ion conduction at the interface. At room temp., all-solid-state cells with Li2SiO3-coated LiCoO2 were discharged even under the high c.d. of 6.4 mA/cm2.
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Yamada, H.; Oga, Y.; Saruwatari, I.; Moriguchi, I. Local Structure and Ionic Conduction at Interfaces of Electrode and Solid Electrolytes. J. Electrochem. Soc. 2012, 159, A380– A385, DOI: 10.1149/2.035204jes
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15
Local structure and ionic conduction at interfaces of electrode and solid electrolytes
Yamada, Hirotsohi; Oga, Yusuke; Saruwatari, Isamu; Moriguchi, Isamu
Journal of the Electrochemical Society (2012), 159 (4), A380-A385CODEN: JESOAN; ISSN:0013-4651. (Electrochemical Society)
All solid state batteries are attracting interests as next generation energy storage devices. However, little is known about interfaces between active materials and solid electrolytes, which may affect performance of the devices. Interfacial phenomena between electrodes and solid electrolytes of all solid state batteries were studied by using nanocomposites of Li2SiO3-TiO2, Li2SiO3-LiTiO2, and Li2SiO3-FePO4. Studies on ionic cond. of these composites revealed Li ion transfer across the interfaces without elec. field, which depended on electrode potentials. For Li2SiO3-TiO2, cond. of the composites was enhanced by addn. of TiO2 and well explained by space charge layer model. With LiTiO2 which shows lower electrode potential, the cond. was deteriorated due to decrease in vacancies in Li2SiO3. At the interface of Li2SiO3-FePO4, a lot of Li ions in Li2SiO3 are trapped at the interface or maybe are inserted into FePO4, resulting in many vacancies in Li2SiO3 and lattice distortion. The results show the ionic conduction at the interface is strongly affected by the electrode potential and the importance of design of interfaces of all solid state batteries is pointed out.
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Takada, K. Interfacial Nanoarchitectonics for Solid-State Lithium Batteries. Langmuir 2013, 29, 7538– 7541, DOI: 10.1021/la3045253
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Interfacial Nanoarchitectonics for Solid-State Lithium Batteries
Takada, Kazunori
Langmuir (2013), 29 (24), 7538-7541CODEN: LANGD5; ISSN:0743-7463. (American Chemical Society)
A review of interfacial structures in lithium batteries that lower the interfacial resistance to enable high-power interfaces by controlling the carrier d. Strong demand for solid-state Li batteries has prompted intensive research for achieving fast ionic conduction in solids. Although the highest cond. found among sulfides is higher than that of liq. electrolytes, it improves the battery performance only in combination with electrodes via a low-resistance interface.
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Takada, K.; Ohta, N.; Zhang, L.; Xu, X.; Hang, B. T.; Ohnishi, T.; Osada, M.; Sasaki, T. Interfacial phenomena in solid-state lithium battery with sulfide solid electrolyte. Solid State Ionics 2012, 225, 594– 597, DOI: 10.1016/j.ssi.2012.01.009
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Interfacial phenomena in solid-state lithium battery with sulfide solid electrolyte
Takada, Kazunori; Ohta, Narumi; Zhang, Lianqi; Xu, Xiaoxiong; Hang, Bui Thi; Ohnishi, Tsuyoshi; Osada, Minoru; Sasaki, Takayoshi
Solid State Ionics (2012), 225 (), 594-597CODEN: SSIOD3; ISSN:0167-2738. (Elsevier B.V.)
The effects of surface coating on electrode properties of LiMn2O4 in a sulfide solid electrolyte were investigated. The surface coating with LiNbO3 reduced the electrode resistance by two orders of magnitude. Changes in the electrode properties were very similar to those obsd. for the corresponding LiCoO2 electrodes, which strongly suggest that the space-charge layer formed at the high-voltage cathode/sulfide electrolyte interface is rate-detg. and must be controlled to improve the rate capability.
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Sakuda, A.; Hayashi, A.; Tatsumisago, M. Interfacial Observation between LiCoO₂ Electrode and Li₂S–P₂S₅ Solid Electrolytes of All-Solid-State Lithium Secondary Batteries Using Transmission Electron Microscopy. Chem. Mater. 2010, 22, 949– 956, DOI: 10.1021/cm901819c
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Interfacial Observation between LiCoO2 Electrode and Li2S-P2S5 Solid Electrolytes of All-Solid-State Lithium Secondary Batteries using Transmission Electron Microscopy
Sakuda, Atsushi; Hayashi, Akitoshi; Tatsumisago, Masahiro
Chemistry of Materials (2010), 22 (3), 949-956CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
In all-solid-state lithium secondary batteries, both the electrode and electrolyte materials are solid. The electrode and solid electrolyte interface structure and morphol. affect a battery electrochem. performance. Observation of the interface between LiCoO2 cathode and highly lithium-ion-conducting Li2S-P2S5 solid electrolyte was conducted using transmission electron microscopy. An interfacial layer was formed at the interface between LiCoO2 electrode and Li2S-P2S5 solid electrolyte after the battery initial charge. Furthermore, mutual diffusions of Co, P, and S at the interface between LiCoO2 and Li2S-P2S5 were obsd. The mutual diffusion and the formation of the interfacial layer were suppressed using LiCoO2 particles coated with Li2SiO3 thin film. Results showed that all-solid-state batteries using Li2SiO3-coated LiCoO2 had better electrochem. performance than those using non-coated LiCoO2. The all-solid-state batteries functioned at -30°. Moreover, the all-solid-state battery using Li2SiO3-coated LiCoO2 was charged and discharged under a high c.d. of 40 mA/cm2 at 100°.
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Ohtomo, T.; Hayashi, A.; Tatsumisago, M.; Tsuchida, Y.; Hama, S.; Kawamoto, K. All-solid-state lithium secondary batteries using the 75Li₂S·25P₂S₅ glass and the 70Li₂S·30P₂S₅ glass–ceramic as solid electrolytes. J. Power Sources 2013, 233, 231– 235, DOI: 10.1016/j.jpowsour.2013.01.090
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All-solid-state lithium secondary batteries using the 75Li2S·25P2S5 glass and the 70Li2S·30P2S5 glass-ceramic as solid electrolytes
Ohtomo, Takamasa; Hayashi, Akitoshi; Tatsumisago, Masahiro; Tsuchida, Yasushi; Hama, Shigenori; Kawamoto, Koji
Journal of Power Sources (2013), 233 (), 231-235CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)
The 70Li2S·30P2S5 glass-ceramic showed high ion cond. of 1.5 × 10-3 S cm-1 at room temp. The 75Li2S·25P2S5 glass showed ion cond. of 5.0 × 10-4 S cm-1 at room temp. and high chem. stability. All-solid-state C/LiCoO2 cells using those materials as solid electrolytes were assembled. Their cell performance were compared. The cell using the 70Li2S·30P2S5 glass-ceramic showed superior rate performance to the cell using the 75Li2S·25P2S5 glass. On the other hand, the cell using the 75Li2S·25P2S5 glass showed superior cycle performance to the cell using the 70Li2S·30P2S5 glass-ceramic. It was suggested that solid electrolytes in all-solid-state batteries preferably had both high ion cond. and high chem. stability.
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Woo, H. J.; Trevey, J. E.; Cavanagh, A. S.; Choi, Y. S.; Kim, S. C.; George, S. M.; Oh, K. H.; Lee, S. H. Nanoscale Interface Modification of LiCoO₂ by Al₂O₃ Atomic Layer Deposition for Solid-State Li Batteries. J. Electrochem. Soc. 2012, 159, A1120– A1124, DOI: 10.1149/2.085207jes
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20
Nanoscale interface modification of LiCoO2 by Al2O3 atomic layer deposition for solid-state Li batteries
Woo, Jae Ha; Trevey, James E.; Cavanagh, Andrew S.; Choi, Yong Seok; Kim, Seul Cham; George, Steven M.; Oh, Kyu Hwan; Lee, Se-Hee
Journal of the Electrochemical Society (2012), 159 (7), A1120-A1124CODEN: JESOAN; ISSN:0013-4651. (Electrochemical Society)
Cycle stability of solid-state lithium batteries (SSLBs) using a LiCoO2 cathode is improved by at. layer deposition (ALD) on active material powder with Al2O3. SSLBs with LiCoO2/Li3.15Ge0.15P0.85S4/77.5Li2S-22.5P2S5/Li structure were constructed and tested by charge-discharge cycling at a c.d. of 45 μA cm-2 with a voltage window of 3.3 ∼ 4.3 V (vs. Li/Li+). Capacity degrdn. during cycling is suppressed dramatically by employing Al2O3 ALD-coated LiCoO2 in the composite cathode. Whereas only 70% of capacity retention is achieved for uncoated LiCoO2 after 25 cycles, 90% of capacity retention is obsd. for LiCoO2 with ALD Al2O3 layers. Electrochem. impedance spectroscopy (EIS) and transmission electron microscopy (TEM) studies show that the presence of ALD Al2O3 layers on the surface of LiCoO2 reduces interfacial resistance development between LiCoO2 and solid state electrolyte (SSE) during cycling.
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Haruyama, J.; Sodeyama, K.; Han, L.; Takada, K.; Tateyama, Y. Space–Charge Layer Effect at Interface between Oxide Cathode and Sulfide Electrolyte in All-Solid-State Lithium-Ion Battery. Chem. Mater. 2014, 26, 4248– 4255, DOI: 10.1021/cm5016959
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Space-Charge Layer Effect at Interface between Oxide Cathode and Sulfide Electrolyte in All-Solid-State Lithium-Ion Battery
Haruyama, Jun; Sodeyama, Keitaro; Han, Liyuan; Takada, Kazunori; Tateyama, Yoshitaka
Chemistry of Materials (2014), 26 (14), 4248-4255CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
The authors theor. elucidated the characteristics of the space-charge layer (SCL) at interfaces between oxide cathode and sulfide electrolyte in all-solid-state Li-ion batteries (ASS-LIBs) and the effect of the buffer layer interposition, for the 1st time, via the calcns. with d. functional theory (DFT) + U framework. As a most representative system, the authors examd. the interfaces between LiCoO2 cathode and β-Li3PS4 solid electrolyte (LCO/LPS), and the LiCoO2/LiNbO3/β-Li3PS4 (LCO/LNO/LPS) interfaces with the LiNbO3 buffer layers. The DFT+U calcns., coupling with a systematic procedure for interface matching, showed the stable structures and the electronic states of the interfaces. The LCO/LPS interface has attractive Li adsorption sites and rather disordered structure, whereas the interposition of the LNO buffer layers forms smooth interfaces without Li adsorption sites for both LCO and LPS sides. The calcd. energies of the Li-vacancy formation and the Li migration reveal that subsurface Li in the LPS side can begin to transfer at the under-voltage condition in the LCO/LPS interface, which suggests the SCL growth at the beginning of charging, leading to the interfacial resistance. The LNO interposition suppresses this growth of SCL and provides smooth Li transport paths free from the possible bottlenecks. These aspects on the at. scale will give a useful perspective for the further improvement of the ASS-LIB performance.
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Haruyama, J.; Sodeyama, K.; Tateyama, Y. Cation Mixing Properties toward Co Diffusion at the LiCoO₂ Cathode/Sulfide Electrolyte Interface in a Solid-State Battery. ACS Appl. Mater. Interfaces 2017, 9, 286– 292, DOI: 10.1021/acsami.6b08435
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Cation Mixing Properties toward Co Diffusion at the LiCoO2 Cathode/Sulfide Electrolyte Interface in a Solid-State Battery
Haruyama, Jun; Sodeyama, Keitaro; Tateyama, Yoshitaka
ACS Applied Materials & Interfaces (2017), 9 (1), 286-292CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
All-solid-state Li-ion batteries (ASS-LIBs) are expected to be the next-generation battery, however, their large interfacial resistance hinders their widespread application. To understand and resolve the possible causes of this resistance, we examd. mutual diffusion properties of the cation elements at LiCoO2 (LCO) cathode/β-Li3PS4 (LPS) solid electrolyte interface as a representative system as well as the effect of a LiNbO3 buffer layer by first-principles calcns. Evaluating energies of exchanging ions between the cathode and the electrolyte, we found that the mixing of Co and P is energetically preferable to the unmixed states at the LCO/LPS interface. We also demonstrated that the interposition of the buffer layer suppresses such mixing because the exchange of Co and Nb is energetically unfavorable. Detailed analyses of the defect levels and the exchange energies by using the individual bulk crystals as well as the interfaces suggest that the lower interfacial states in the energy gap can make a major contribution to the stabilization of the Co - P exchange, although the anion bonding preference of Co and P as well as the electrostatic interactions may have effects as well. Finally, the Co - P exchanges induce interfacial Li sites with low chem. potentials, which enhance the growth of the Li depletion layer. These atomistic understandings can be meaningful for the development of ASS-LIBs with smaller interfacial resistances.
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Tateyama, Y.; Gao, B.; Jalem, R.; Haruyama, J. Theoretical picture of positive electrode–solid electrolyte interface in all-solid-state battery from electrochemistry and semiconductor physics viewpoints. Curr. Opin. Electrochem. 2019, 17, 149– 157, DOI: 10.1016/j.coelec.2019.06.003
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Theoretical picture of positive electrode-solid electrolyte interface in all-solid-state battery from electrochemistry and semiconductor physics viewpoints
Tateyama, Yoshitaka; Gao, Bo; Jalem, Randy; Haruyama, Jun
Current Opinion in Electrochemistry (2019), 17 (), 149-157CODEN: COEUCY; ISSN:2451-9111. (Elsevier B.V.)
All-solid-state battery has attracted significant attention as a promising next-generation energy storage. However, interfacial resistance of ion transport between the pos. electrode and solid electrolyte is still a crucial issue for the all-solid-state battery commercialization. Although some mechanisms such as space charge layer and reaction layer effects have been suggested, the ionic and electronic behaviors at the solid-solid interfaces have not yet been fully elucidated. Here, we address theor. microscopic understanding of the interfacial ionics and electronics from the viewpoints of electrochem. and semiconductor physics, in conjunction with the results of recent d. functional theory calcns.
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Gao, B.; Jalem, R.; Ma, Y.; Tateyama, Y. Li⁺ Transport Mechanism at the Heterogeneous Cathode/Solid Electrolyte Interface in an All-Solid-State Battery via the First-Principles Structure Prediction Scheme. Chem. Mater. 2020, 32, 85– 96, DOI: 10.1021/acs.chemmater.9b02311
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Li+ Transport Mechanism at the Heterogeneous Cathode/Solid Electrolyte Interface in an All-Solid-State Battery via the First-Principles Structure Prediction Scheme
Gao, Bo; Jalem, Randy; Ma, Yanming; Tateyama, Yoshitaka
Chemistry of Materials (2020), 32 (1), 85-96CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
High interfacial resistance between a cathode and solid electrolyte (SE) has been a long-standing problem for all-solid-state batteries (ASSBs). Though thermodn. approaches suggested possible phase transformations at the interfaces, direct analyses of the ionic and electronic states at the solid/solid interfaces are still crucial. Here, newly constructed scheme is used for predicting heterogeneous interface structures via the swarm-intelligence-based crystal structure anal. by particle swarm optimization method, combined with d. functional theory calcns., and systematically investigated the mechanism of Li-ion (Li+) transport at the interface in LiCoO2 cathode/β-Li3PS4 SE, a representative ASSB system. The sampled favorable interface structures indicate that the interfacial reaction layer is formed with both mixing of Co and P cations and mixing of O and S anions. The calcd. site-dependent Li chem. potentials μLi(r) and potential energy surfaces for Li+ migration across the interfaces reveal that interfacial Li+ sites with higher μLi(r) values cause dynamic Li+ depletion with the interfacial electron transfer in the initial stage of charging. The Li+-depleted space can allow oxidative decompn. of SE materials. These pieces of evidence theor. confirm the primary origin of the obsd. interfacial resistance in ASSBs and the mechanism of the resistance decrease obsd. with oxide buffer layers (e.g., LiNbO3) and oxide SE. The present study also provides a perspective for the structure sampling of disordered heterogeneous solid/solid interfaces on the at. scale.
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Haruta, M.; Shiraki, S.; Suzuki, T.; Kumatani, A.; Ohsawa, T.; Takagi, Y.; Shimizu, R.; Hitosugi, T. Negligible “Negative Space-Charge Layer Effects” at Oxide-Electrolyte/Electrode Interfaces of Thin-Film Batteries. Nano Lett. 2015, 15, 1498– 1502, DOI: 10.1021/nl5035896
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Negligible "Negative Space-Charge Layer Effects" at Oxide-Electrolyte/Electrode Interfaces of Thin-Film Batteries
Haruta, Masakazu; Shiraki, Susumu; Suzuki, Tohru; Kumatani, Akichika; Ohsawa, Takeo; Takagi, Yoshitaka; Shimizu, Ryota; Hitosugi, Taro
Nano Letters (2015), 15 (3), 1498-1502CODEN: NALEFD; ISSN:1530-6984. (American Chemical Society)
In this paper, the surprisingly low electrolyte/electrode interface resistance of 8.6 Ω cm2 obsd. in thin-film batteries is reported. This value is an order of magnitude smaller than that presented in previous reports on all-solid-state lithium batteries. The value is also smaller than that found in a liq. electrolyte-based batteries. The low interface resistance indicates that the neg. space-charge layer effects at the Li3PO4-xNx/LiCoO2 interface are negligible and demonstrates that it is possible to fabricate all-solid state batteries with faster charging/discharging properties.
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Kawasoko, H.; Shiraki, S.; Suzuki, T.; Shimizu, R.; Hitosugi, T. Extremely Low Resistance of Li₃PO₄ Electrolyte/Li(Ni_0.5Mn_1.5)O₄ Electrode Interfaces. ACS Appl. Mater. Interfaces 2018, 10, 27498– 27502, DOI: 10.1021/acsami.8b08506
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Extremely Low Resistance of Li3PO4 Electrolyte/Li(Ni0.5Mn1.5)O4 Electrode Interfaces
Kawasoko, Hideyuki; Shiraki, Susumu; Suzuki, Toru; Shimizu, Ryota; Hitosugi, Taro
ACS Applied Materials & Interfaces (2018), 10 (32), 27498-27502CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
Solid-state Li batteries contg. Li(Ni0.5Mn1.5)O4 as a 5 V-class pos. electrode are expected to revolutionize mobile devices and elec. vehicles. However, practical applications of such batteries are hampered by the high resistance at their solid electrolyte/electrode interfaces. Here, an extremely low electrolyte/electrode interface resistance of 7.6 Ω cm2 is achieved in solid-state Li batteries with Li(Ni0.5Mn1.5)O4. Furthermore, spontaneous migration is obsd. of Li ions from the solid electrolyte to the pos. electrode after the formation of the electrolyte/electrode interface. Finally, stable fast charging and discharging is demonstrated of the solid-state Li batteries at a c.d. of 14 mA/cm2. These results provide a solid foundation to understand and fabricate low-resistance electrolyte/electrode interfaces.
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Sharafi, A.; Kazyak, E.; Davis, A. L.; Yu, S.; Thompson, T.; Siegel, D. J.; Dasgupta, N. P.; Sakamoto, J. Surface Chemistry Mechanism of Ultra-Low Interfacial Resistance in the Solid-State Electrolyte Li₇La₃Zr₂O₁₂. Chem. Mater. 2017, 29, 7961– 7968, DOI: 10.1021/acs.chemmater.7b03002
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Surface Chemistry Mechanism of Ultra-Low Interfacial Resistance in the Solid-State Electrolyte Li7La3Zr2O12
Sharafi, Asma; Kazyak, Eric; Davis, Andrew L.; Yu, Seungho; Thompson, Travis; Siegel, Donald J.; Dasgupta, Neil P.; Sakamoto, Jeff
Chemistry of Materials (2017), 29 (18), 7961-7968CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
The impact of surface chem. on the interfacial resistance between the Li7La3Zr2O12 (LLZO) solid-state electrolyte and a metallic Li electrode is revealed. Control of surface chem. allows the interfacial resistance to be reduced to 2 Ω cm2, lower than that of liq. electrolytes, without the need for interlayer coatings. A mechanistic understanding of the origins of ultra-low resistance is provided by quant. evaluating the linkages between interfacial chem., Li wettability, and electrochem. phenomena. A combination of Li contact angle measurements, XPS, first-principles calcns., and impedance spectroscopy demonstrates that the presence of common LLZO surface contaminants, Li2CO3 and LiOH, result in poor wettability by Li and high interfacial resistance. On the basis of this mechanism, a simple procedure for removing these surface layers is demonstrated, which results in a dramatic increase in Li wetting and the elimination of nearly all interfacial resistance. The low interfacial resistance is maintained over one-hundred cycles and suggests a straightforward pathway to achieving high energy and power d. solid-state batteries.
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Zhu, Y.; He, X.; Mo, Y. Origin of Outstanding Stability in the Lithium Solid Electrolyte Materials: Insights from Thermodynamic Analyses Based on First-Principles Calculations. ACS Appl. Mater. Interfaces 2015, 7, 23685– 23693, DOI: 10.1021/acsami.5b07517
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Origin of Outstanding Stability in the Lithium Solid Electrolyte Materials: Insights from Thermodynamic Analyses Based on First-Principles Calculations
Zhu, Yizhou; He, Xingfeng; Mo, Yifei
ACS Applied Materials & Interfaces (2015), 7 (42), 23685-23693CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
First-principles calcns. were performed to investigate the electrochem. stability of lithium solid electrolyte materials in all-solid-state Li-ion batteries. The common solid electrolytes were found to have a limited electrochem. window. The results suggest that the outstanding stability of the solid electrolyte materials is not thermodynamically intrinsic but is originated from kinetic stabilizations. The sluggish kinetics of the decompn. reactions cause a high overpotential leading to a nominally wide electrochem. window obsd. in many expts. The decompn. products, similar to the solid-electrolyte-interphases, mitigate the extreme chem. potential from the electrodes and protect the solid electrolyte from further decompns. With the aid of the first-principles calcns., the passivation mechanism is revealed of these decompn. interphases and quantified the extensions of the electrochem. window from the interphases. It was also found that the artificial coating layers applied at the solid electrolyte and electrode interfaces have a similar effect of passivating the solid electrolyte. The newly gained understanding provided general principles for developing solid electrolyte materials with enhanced stability and for engineering interfaces in all-solid-state Li-ion batteries.
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Zhu, Y.; He, X.; Mo, Y. First principles study on electrochemical and chemical stability of solid electrolyte–electrode interfaces in all-solid-state Li-ion batteries. J. Mater. Chem. A 2016, 4, 3253– 3266, DOI: 10.1039/C5TA08574H
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First principles study on electrochemical and chemical stability of solid electrolyte-electrode interfaces in all-solid-state Li-ion batteries
Zhu, Yizhou; He, Xingfeng; Mo, Yifei
Journal of Materials Chemistry A: Materials for Energy and Sustainability (2016), 4 (9), 3253-3266CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)
All-solid-state Li-ion batteries based on ceramic solid electrolyte materials are a promising next-generation energy storage technol. with high energy d. and enhanced cycle life. The poor interfacial conductance is one of the key limitations in enabling all-solid-state Li-ion batteries. However, the origin of this poor conductance has not been understood, and there is limited knowledge about the solid electrolyte-electrode interfaces in all-solid-state Li-ion batteries. In this study, we performed first principles calcns. to evaluate the thermodn. of the interfaces between solid electrolyte and electrode materials and to identify the chem. and electrochem. stabilities of these interfaces. Our computation results reveal that many solid electrolyte-electrode interfaces have limited chem. and electrochem. stability, and that the formation of interphase layers is thermodynamically favorable at these interfaces. These formed interphase layers with different properties significantly affect the electrochem. performance of all-solid-state Li-ion batteries. The mechanisms of applying interfacial coating layers to stabilize the interface and to reduce interfacial resistance are illustrated by our computation. This study demonstrates a computational scheme to evaluate the chem. and electrochem. stability of heterogeneous solid interfaces. The enhanced understanding of the interfacial phenomena provides the strategies of interface engineering to improve performances of all-solid-state Li-ion batteries.
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Richards, W. D.; Miara, L. J.; Wang, Y.; Kim, J. C.; Ceder, G. Interface Stability in Solid-State Batteries. Chem. Mater. 2016, 28, 266– 273, DOI: 10.1021/acs.chemmater.5b04082
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Interface Stability in Solid-State Batteries
Richards, William D.; Miara, Lincoln J.; Wang, Yan; Kim, Jae Chul; Ceder, Gerbrand
Chemistry of Materials (2016), 28 (1), 266-273CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
Development of high cond. solid-state electrolytes for lithium ion batteries has proceeded rapidly in recent years, but incorporating these new materials into high-performing batteries has proven difficult. Interfacial resistance is now the limiting factor in many systems, but the exact mechanisms of this resistance have not been fully explained - in part because exptl. evaluation of the interface can be very difficult. In this work, we develop a computational methodol. to examine the thermodn. of formation of resistive interfacial phases. The predicted interfacial phase formation is well correlated with exptl. interfacial observations and battery performance. We calc. that thiophosphate electrolytes have esp. high reactivity with high voltage cathodes and a narrow electrochem. stability window. We also find that a no. of known electrolytes are not inherently stable but react in situ with the electrode to form passivating but ionically conducting barrier layers. As a ref. for experimentalists, we tabulate the stability and expected decompn. products for a wide range of electrolyte, coating, and electrode materials including a no. of high-performing combinations that have not yet been attempted exptl.
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Deng, Z.; Zhu, Z.; Chu, L.-H.; Ong, S.-P. Data-Driven First-Principles Methods for the Study and Design of Alkali Superionic Conductors. Chem. Mater. 2017, 29, 281– 288, DOI: 10.1021/acs.chemmater.6b02648
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Data-Driven First-Principles Methods for the Study and Design of Alkali Superionic Conductors
Deng, Zhi; Zhu, Zhuoying; Chu, Iek-Heng; Ong, Shyue Ping
Chemistry of Materials (2017), 29 (1), 281-288CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
A detailed exposition of how first-principles methods can be used to guide alkali superionic conductor (ASIC) study and design is presented. Using the argyrodite Li6PS5Cl as a case study, it is demonstrated how modern information technol. (IT) infrastructure and software tools can facilitate the assessment of alkali superionic conductors in terms of various crit. properties of interest such as phase and electrochem. stability and ionic cond. The emphasis is on well-documented, reproducible anal. code that can be readily generalized to other material systems and design problems. For our chosen Li6PS5Cl case study material, it is shown that Li excess is crucial to enhancing its cond. by increasing the occupancy of interstitial sites that promote long-range Li+ diffusion between cage-like frameworks. The predicted room-temp. conductivities and activation barriers are in reasonably good agreement with exptl. values.
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Miara, L. J.; Richards, W. D.; Wang, Y. E.; Ceder, G. First-Principles Studies on Cation Dopants and Electrolyte|Cathode Interphases for Lithium Garnets. Chem. Mater. 2015, 27, 4040– 4047, DOI: 10.1021/acs.chemmater.5b01023
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First-Principles Studies on Cation Dopants and Electrolyte|Cathode Interphases for Lithium Garnets
Miara, Lincoln J.; Richards, William Davidson; Wang, Yan E.; Ceder, Gerbrand
Chemistry of Materials (2015), 27 (11), 4040-4047CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
Lithium garnet with the formula Li7La3Zr2O12 (LLZO) has many properties of an ideal electrolyte in all-solid state lithium batteries. However, internal resistance in batteries utilizing these electrolytes remains high. For widespread adoption, the LLZO's internal resistance must be lowered by increasing its bulk cond., reducing grain boundary resistance, and/or pairing it with an appropriate cathode to minimize interfacial resistance. Cation doping has been shown to be crucial in LLZO to stabilize the higher cond. cubic structure, yet there is still little understanding about which cations have high soly. in LLZO. In this work, d. functional theory (DFT) is used to calc. the defect energies and site preference of all possible dopants in these materials. The findings suggest several novel dopants such as Zn2+ and Mg2+ predicted to be stable on the Li- and Zr-sites, resp. To understand the source of interfacial resistance between the electrolyte and the cathode, the thermodn. stability is investigated of the electrolyte|cathode interphase, calcg. the reaction energy for LLMO (M = Zr, Ta) against LiCoO2, LiMnO2, and LiFePO4 (LCO, LMO, and LFP, resp.) cathodes over the voltage range seen in lithium-ion battery operation. The results suggest that, for LLZO, the LLZO|LCO is the most stable, showing only a low driving force for decompn. in the charged state into La2O3, La2Zr2O7, and Li2CoO3, while the LLZO|LFP appears to be the most reactive, forming Li3PO4, La2Zr2O7, LaFeO3, and Fe2O3. These results provide a ref. for use by researchers interested in bonding these electrolytes to cathodes.
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Tang, H.; Deng, Z.; Lin, Z.; Wang, Z.; Chu, I.-H.; Chen, C.; Zhu, Z.; Zheng, C.; Ong, S. P. Probing Solid–Solid Interfacial Reactions in All-Solid-State Sodium-Ion Batteries with First-Principles Calculations. Chem. Mater. 2018, 30, 163– 173, DOI: 10.1021/acs.chemmater.7b04096
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Probing Solid-Solid Interfacial Reactions in All-Solid-State Sodium-Ion Batteries with First-Principles Calculations
Tang, Hanmei; Deng, Zhi; Lin, Zhuonan; Wang, Zhenbin; Chu, Iek-Heng; Chen, Chi; Zhu, Zhuoying; Zheng, Chen; Ong, Shyue Ping
Chemistry of Materials (2018), 30 (1), 163-173CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
We present an exposition of first-principles approaches to elucidating interfacial reactions in all-solid-state sodium-ion batteries. We will demonstrate how thermodn. approxns. based on assumptions of fast alkali diffusion and multispecies equil. can be used to effectively screen combinations of Na-ion electrodes, solid electrolytes, and buffer oxides for electrochem. and chem. compatibility. We find that exchange reactions, esp. between simple oxides and thiophosphate groups to form PO43-, are the main cause of large driving forces for cathode/solid electrolyte interfacial reactions. A high reactivity with large vol. changes is also predicted at the Na anode/solid electrolyte interface, while the Na2Ti3O7 anode is predicted to be much more stable against a broad range of solid electrolytes. We identify several promising binary oxides, Sc2O3, SiO2, TiO2, ZrO2, and HfO2, that are similarly or more chem. compatible with most electrodes and solid electrolytes than the commonly used Al2O3 is. Finally, we show that ab initio mol. dynamics simulations of the NaCoO2/Na3PS4 interface model predict that the formation of SO42--contg. compds. and Na3P is kinetically favored over the formation of PO43--contg. compds., in contrast to the predictions of the thermodn. models. This work provides useful insights into materials selection strategies for enabling stable electrode/solid electrolyte interfaces, a crit. bottleneck in designing all-solid-state sodium-ion batteries, and outlines several testable predictions for future exptl. validation.
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Du, Y. A.; Holzwarth, N. A. W. Mechanisms of Li⁺ diffusion in crystalline γ^– and β–Li₃PO₄ electrolytes from first principles. Phys. Rev. B 2007, 76, 174302, DOI: 10.1103/PhysRevB.76.174302
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Mechanisms of Li+ diffusion in crystalline γ- and β-Li3PO4 electrolytes from first principles
Du, Yaojun A.; Holzwarth, N. A. W.
Physical Review B: Condensed Matter and Materials Physics (2007), 76 (17), 174302/1-174302/14CODEN: PRBMDO; ISSN:1098-0121. (American Physical Society)
Recently, there was significant interest in developing solid-state lithium ion electrolytes for use in batteries and related technologies. The authors used 1st-principles modeling techniques based on d.-functional theory and the nudged elastic band method to examine possible Li ion diffusion mechanisms in idealized crystals of the electrolyte material Li3PO4 in both the γ and β cryst. forms, considering both vacancy and interstitial processes to find the migration energies Em. Interstitial diffusion via an interstitialcy mechanism involving the concerted motion of an interstitial Li ion and a neighboring lattice Li ion may provide the most efficient ion transport in Li3PO4. Ion transport in undoped crystals depends on the formation of vacancy-interstitial pairs requiring an addnl. energy Ef, which results in a thermal activation energy EA = Em + Ef/2. The calcd. values of EA are in excellent agreement with single crystal measurements on γ-Li3PO4. The results examine the similarities and differences between the diffusion processes in the γ and β crystal structures. The authors analyze the zone center phonon modes in both crystals to further validate the calcns. with exptl. measurements and to det. the range of vibrational frequencies assocd. with Li ion motions which might contribute to the diffusion processes.
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Leung, K. DFT modelling of explicit solid–solid interfaces in batteries: methods and challenges. Phys. Chem. Chem. Phys. 2020, 22, 10412– 10425, DOI: 10.1039/C9CP06485K
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DFT modelling of explicit solid-solid interfaces in batteries: methods and challenges
Leung, Kevin
Physical Chemistry Chemical Physics (2020), 22 (19), 10412-10425CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)
D. Functional Theory (DFT) calcns. of electrode material properties in high energy d. storage devices like lithium batteries have been std. practice for decades. In contrast, DFT modeling of explicit interfaces in batteries arguably lacks universally adopted methodol. and needs further conceptual development. In this paper, we focus on solid-solid interfaces, which are ubiquitous not just in all-solid state batteries; liq.-electrolyte-based batteries often rely on thin, solid passivating films on electrode surfaces to function. We use metal anode calcns. to illustrate that explicit interface models are crit. for elucidating contact potentials, elec. fields at interfaces, and kinetic stability with respect to parasitic reactions. The examples emphasize three key challenges: (1) the "dirty" nature of most battery electrode surfaces; (2) voltage calibration and control; and (3) the fact that interfacial structures are governed by kinetics, not thermodn. To meet these challenges, developing new computational techniques and importing insights from other electrochem. disciplines will be beneficial.
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Sumita, M.; Tanaka, Y.; Ikeda, M.; Ohno, T. Charged and Discharged States of Cathode/Sulfide Electrolyte Interfaces in All-Solid-State Lithium Ion Batteries. J. Phys. Chem. C 2016, 120, 13332– 13339, DOI: 10.1021/acs.jpcc.6b01207
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Charged and Discharged States of Cathode/Sulfide Electrolyte Interfaces in All-Solid-State Lithium Ion Batteries
Sumita, Masato; Tanaka, Yoshinori; Ikeda, Minoru; Ohno, Takahisa
Journal of Physical Chemistry C (2016), 120 (25), 13332-13339CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)
Interfaces between cathodes and sulfide electrolytes exhibit high resistance in all-solid-state lithium ion batteries. In this paper, to elucidate the origin of the high interface resistance we have theor. investigated the properties of the cathode interfaces with the sulfide electrolyte and oxide electrolyte for comparison. From the d. functional mol. dynamics simulations of the LiFePO4/Li3PS4 interface in both discharged and charged states, we have demonstrated the instability of the sulfide interface in the charged state, i.e., the lithium depletion and oxidn. on the sulfide side near the interface, in contrast to the oxide interfaces. The obtained results imply the formation of a Li-depleted layer around the sulfide interfaces during charging and support the validity of the insertion of oxide buffer layers at the interface to reduce the interface resistance.
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Kramer, D.; Ceder, G. Tailoring the Morphology of LiCoO₂: A First Principles Study. Chem. Mater. 2009, 21, 3799– 3809, DOI: 10.1021/cm9008943
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Tailoring the Morphology of LiCoO2: A First Principles Study
Kramer, Denis; Ceder, Gerbrand
Chemistry of Materials (2009), 21 (16), 3799-3809CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
Surface energies of several low-index surfaces of layered LiCoO2 were studied as a function of the external Li and O chem. potentials by First Principles calcns. in the generalized gradient approxn. (GGA) to d. functional theory (DFT), treating on-site electron correlation within the DFT+U framework. The set of surfaces contained in the equil. shape depended on the environment. The (0001) and (10‾14) surfaces were present for all reasonable values of the Li and O chem. potentials. The (01‾12) surface, however, is stable only under oxidizing conditions. The equil. shape is sensitive to the equilibration environment because the thermodynamically favorable surface terminations and surface energies of the polar (0001) and (01‾12) surfaces are a function of the environment. This provides a lever to tailor the crystal shape according to application requirements (e.g., as active material in Li-ion batteries).
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Shao-Horn, Y.; Croguennec, L.; Delmas, C.; Nelson, E. C.; O’keefe, M. A. Atomic resolution of lithium ions in LiCoO₂. Nat. Mater. 2003, 2, 464– 467, DOI: 10.1038/nmat922
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Atomic resolution of lithium ions in LiCoO2
Shao-Horn Yang; Croguennec Laurence; Delmas Claude; Nelson E Chris; O'Keefe Michael A
Nature materials (2003), 2 (7), 464-7 ISSN:1476-1122.
LiCoO2 is the most common lithium storage material for lithium rechargeable batteries, used widely to power portable electronic devices such as laptop computers. Operation of lithium rechargeable batteries is dependent on reversible lithium insertion and extraction processes into and from the host materials of lithium storage. Ordering of lithium and vacancies has a profound effect on the physical properties of the host materials and the electrochemical performance of lithium batteries. However, probing lithium ions has been difficult when using traditional X-ray and neutron powder diffraction techniques due to lithium's relatively low scattering power when compared with those of oxygen and transition metals. In the work presented here, we have succeeded in simultaneously resolving columns of cobalt, oxygen and lithium atoms in layered LiCoO2 battery material, using experimental focal series of LiCoO2 images obtained at sub-angstrom resolution in a mid-voltage transmission electron microscope. Lithium atoms are the smallest and lightest metal atoms, and scatter electrons only very weakly. We believe our observations of lithium to be the first by electron microscopy, and that they show promise for direct visualization of the ordering of lithium and vacancies in transition metal oxides.
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Daheron, L.; Martinez, H.; Dedryvere, R.; Baraille, I.; Menetrier, M.; Denage, C.; Delmas, C.; Gonbeau, D. Surface Properties of LiCoO₂ Investigated by XPS Analyses and Theoretical Calculations. J. Phys. Chem. C 2009, 113, 5843– 5852, DOI: 10.1021/jp803266w
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Surface Properties of LiCoO2 Investigated by XPS Analyses and Theoretical Calculations
Daheron, L.; Martinez, H.; Dedryvere, R.; Baraille, I.; Menetrier, M.; Denage, C.; Delmas, C.; Gonbeau, D.
Journal of Physical Chemistry C (2009), 113 (14), 5843-5852CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)
XPS analyses (core peaks and valence spectra), under highly controlled conditions, have been carried out on stoichiometric LiCoO2 and lithium-overstoichiometric Li1+yCo1-yO2-y (y ∼ 0.05) materials, with significant changes obsd. in the oxygen peaks. Indeed, beside the component attributed to the O2- anions of the cryst. network, a second one with variable intensity has been obsd. on the high binding energy side. With the support of ab initio biperiodical calcns. on LiCoO2, we propose that this peculiar oxygen signature is partially assocd., for LiCoO2, to undercoordinated oxygen atoms coming from (0 0 1) oriented surfaces. These surface oxygen anions are significantly less neg. than the ones of the lattice. These results, in conjunction with SEM analyses for the lithium overstoichiometric material (as prepd. and thermally treated), show that the presence of defects (oxygen vacancies) has to also be considered in the overstoichiometric case. As in battery material, all reactions (the intercalation but also the parasitic ones) occur through the surface; characterization of its crystallog. nature (as well as its electronic properties) is a key point to a better understanding and optimization of Li ion batteries.
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Van der Ven, A.; Ceder, G.; Asta, M.; Tepesch, P. D. First-principles theory of ionic diffusion with nondilute carriers. Phys. Rev. B: Condens. Matter Mater. Phys. 2001, 64, 184307, DOI: 10.1103/PhysRevB.64.184307
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40
First-principles theory of ionic diffusion with nondilute carriers
Van der Ven, A.; Ceder, G.; Asta, M.; Tepesch, P. D.
Physical Review B: Condensed Matter and Materials Physics (2001), 64 (18), 184307/1-184307/17CODEN: PRBMDO; ISSN:0163-1829. (American Physical Society)
Many multicomponent materials exhibit significant configurational disorder. Diffusing ions in such materials migrate along a network of sites that have different energies and that are sepd. by configuration dependent activation barriers. We describe a formalism that enables a first-principles calcn. of the diffusion coeff. in solids exhibiting configurational disorder. The formalism involves the implementation of a local cluster expansion to describe the configuration dependence of activation barriers. The local cluster expansion serves as a link between accurate first-principles calcns. of the activation barriers and kinetic Monte Carlo simulations. By introducing a kinetically resolved activation barrier, we show that a cluster expansion for the thermodn. of ionic disorder can be combined with a local cluster expansion to obtain the activation barrier for migration in any configuration. This ensures that in kinetic Monte Carlo simulations, detailed balance is maintained at all times and kinetic quantities can be calcd. in a properly equilibrated thermodn. state. As an example, we apply this formalism for an investigation of lithium diffusion in LixCoO2. A study of the activation barriers in LixCoOx within the local d. approxn. shows that the migration mechanism and activation barriers depend strongly on the local lithium-vacancy arrangement around the migrating lithium ion. By parameterizing the activation barriers with a local cluster expansion and applying it in kinetic Monte Carlo simulations, we predict that lithium diffusion in layered LixCoO2 is mediated by divacancies at all lithium concns. Furthermore, due to a strong concn. dependence of the activation barrier, the predicted diffusion coeff. varies by several orders of magnitude with lithium concn. x.
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Liu, Z.; Fu, W.; Payzant, E. A.; Yu, X.; Wu, Z.; Dudney, N. J.; Kiggans, J.; Hong, K.; Rondinone, A. J.; Liang, C. Anomalous High Ionic Conductivity of Nanoporous β-Li₃PS₄. J. Am. Chem. Soc. 2013, 135, 975– 978, DOI: 10.1021/ja3110895
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41
Anomalous High Ionic Conductivity of Nanoporous β-Li3PS4
Liu, Zengcai; Fu, Wujun; Payzant, E. Andrew; Yu, Xiang; Wu, Zili; Dudney, Nancy J.; Kiggans, Jim; Hong, Kunlun; Rondinone, Adam J.; Liang, Chengdu
Journal of the American Chemical Society (2013), 135 (3), 975-978CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
Lithium-ion-conducting solid electrolytes hold promise for enabling high-energy battery chemistries and circumventing safety issues of conventional lithium batteries. Achieving the combination of high ionic cond. and a broad electrochem. window in solid electrolytes is a grand challenge for the synthesis of battery materials. Herein we show an enhancement of the room-temp. lithium-ion cond. by 3 orders of magnitude through the creation of nanostructured Li3PS4. This material has a wide electrochem. window (5 V) and superior chem. stability against lithium metal. The nanoporous structure of Li3PS4 reconciles two vital effects that enhance the ionic cond.: (a) the redn. of the dimensions to a nanometer-sized framework stabilizes the high-conduction β phase that occurs at elevated temps., and (b) the high surface-to-bulk ratio of nanoporous β-Li3PS4 promotes surface conduction. Manipulating the ionic cond. of solid electrolytes has far-reaching implications for materials design and synthesis in a broad range of applications, including batteries, fuel cells, sensors, photovoltaic systems, and so forth.
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Maruyama, M.; Kanno, R.; Kawamoto, Y.; Kamiyama, T. Structure of the thio-LISICON, Li₄GeS₄. Solid State Ionics 2002, 154–155, 789– 794, DOI: 10.1016/S0167-2738(02)00492-7
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43
Zemann, J. Die Kristallstruktur von Lithiumphosphat, Li₃PO₄. Acta Crystallogr. 1960, 13, 863– 867, DOI: 10.1107/S0365110X60002132
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43
The crystal structure of lithium phosphate, Li3PO4
Zemann, J.
Acta Crystallographica (1960), 13 (), 863-7CODEN: ACCRA9; ISSN:0365-110X.
The crystal structure of orthorhombic Li3PO4 was detd. and carefully refined in the projections parallel to the 2 shortest axes. The important features of the at. arrangement are PO4 groups which are linked together by Li ions in tetrahedral co.ovrddot.ordination.
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Bates, J. B.; Dudney, N. J.; Gruzalski, G. R.; Zuhr, R. A.; Choudhury, A.; Luck, D. F.; Robertson, J. D. Electrical properties of amorphous lithium electrolyte thin films. Solid State Ionics 1992, 53–56, 647– 654, DOI: 10.1016/0167-2738(92)90442-R
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44
Electrical properties of amorphous lithium electrolyte thin films
Bates, J. B.; Dudney, N. J.; Gruzalski, G. R.; Zuhr, R. A.; Choudhury, A.; Luck, C. F.; Robertson, J. D.
Solid State Ionics (1992), 53-56 (Pt. 1), 647-54CODEN: SSIOD3; ISSN:0167-2738.
The impedance of xLi2O-ySiO2·zP2O5 thin films deposited by RF-magnetron sputtering was analyzed using two models in which the frequency dependence of the bulk response was represented by: (1) a Cole-Cole dielec. function and (2) a const. phase angle element. Increases in the cond. with Li2O concn. and with addn. of SiO2 to Li2O-P2O5 compns. are attributed to an increase in Li+ mobility caused by changes in the film structure. A new amorphous oxynitride electrolyte, Li3.3PO3.9N0.17, prepd. by sputtering Li3PO4 in N2, has a cond. at 25° of 2 × 10-6 S/cm and is stable in contact with lithium.
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Bates, J. B.; Dudney, N. J.; Gruzalski, G. R.; Zuhr, R. A.; Choudhury, A.; Luck, D. F.; Robertson, J. D. Fabrication and characterization of amorphous lithium electrolyte thin films and rechargeable thin-film batteries. J. Power Sources 1993, 43, 103– 110, DOI: 10.1016/0378-7753(93)80106-Y
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45
Fabrication and characterization of amorphous lithium electrolyte thin films and rechargeable thin-film batteries
Bates, J. B.; Dudney, N. J.; Gruzalski, G. R.; Zuhr, R. A.; Choudhury, A.; Luck, C. F.; Robertson, J. D.
Journal of Power Sources (1993), 43 (1-3), 103-10CODEN: JPSODZ; ISSN:0378-7753.
Amorphous Li oxide and oxynitride thin films were synthesized by radio-frequency magnetron sputtering of Li silicates and Li phosphates in Ar, Ar + O, Ar + N, or N. The compn., structure, and elec. properties of the films were detd. using ion and electron beam, x-ray, optical, photoelectron, and a.c. impedance techniques. For Li phosphosilicate films, ion cond. ≤1.4 × 10-6 S/cm at 25° was obsd., but none of the films were stable in contact with Li. A thin-film Li P oxynitride electrolyte prepd. by sputtering Li3PO4 in pure N had cond. of 2 × 10-6 S/cm at 25° and excellent long-term stability in contact with Li. Thin-film cells of 1-μm-thick amorphous V2O5 cathode, 1-μm-thick oxynitride electrolyte film, and 5-μm-thick Li anode were cycled between 3.7 and 1.5 V at discharge rate of ≤100 μA/cm2 and charge rate of ≤20 μA/cm2. The open-circuit voltage of 3.6-3.7 V of fully-charged cells remained virtually unchanged after months of storage.
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Ivanov-Shitz, A. K.; Kireev, V. V.; Mel’nikov, O. K.; Demianets, L. N. Growth and ionic conductivity of γ-Li₃PO₄. Crystallogr. Rep. 2001, 46, 864– 867, DOI: 10.1134/1.1405880
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47
Du, Y. A.; Holzwarth, N. A. W. Li Ion Diffusion Mechanisms in the Crystalline Electrolyte γ-Li₃PO₄. J. Electrochem. Soc. 2007, 154, A999– A1004, DOI: 10.1149/1.2772200
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47
Li ion diffusion mechanisms in the crystalline electrolyte γ-Li3PO4
Du, Yaojun A.; Holzwarth, N. A. W.
Journal of the Electrochemical Society (2007), 154 (11), A999-A1004CODEN: JESOAN; ISSN:0013-4651. (Electrochemical Society)
Solid state Li-ion electrolytes are important in batteries and related technologies. The authors used 1st-principles modeling techniques based on DFT and the nudged elastic band method to examine Li ion diffusion mechanisms in idealized crystals of the electrolyte material, Li3PO4. In modeling the Li-ion vacancy diffusion, the authors find direct hopping between neighboring metastable vacancy configurations to have a minimal migration barrier of Em = 0.6 eV. In modeling the Li-ion interstitial diffusion, the authors find an interstices-related mechanism, involving the concerted motion of an interstitial Li-ion and a neighboring Li ion of the host lattice, that can result in a migration barrier as low as Em = 0.2 eV. The minimal formation energy of a Li-ion vacancy-interstitial pair is Ef = 1.6 eV. Assuming the activation energy for intrinsic defects to be given by EA = Em + Ef/2, the calcns. find EA = 1.0-1.2 eV for ionic diffusion in cryst. γ-Li3PO4, in agreement with exptl. values of 1.1-1.3 eV.
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Thangadurai, V.; Narayanan, S.; Pinzaru, D. Garnet-type solid-state fast Li ion conductors for Li batteries: critical review. Chem. Soc. Rev. 2014, 43, 4714– 4727, DOI: 10.1039/c4cs00020j
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48
Garnet-type solid-state fast Li ion conductors for Li batteries: critical review
Thangadurai, Venkataraman; Narayanan, Sumaletha; Pinzaru, Dana
Chemical Society Reviews (2014), 43 (13), 4714-4727CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)
A review. Batteries are electrochem. devices that store elec. energy in the form of chem. energy. Among known batteries, Li ion batteries (LiBs) provide the highest gravimetric and volumetric energy densities, making them ideal candidates for use in portable electronics and plug-in hybrid and elec. vehicles. Conventional LiBs use an org. polymer electrolyte, which exhibits several safety issues including leakage, poor chem. stability and flammability. The use of a solid-state (ceramic) electrolyte to produce all-solid-state LiBs can overcome all of the above issues. Also, solid-state Li batteries can operate at high voltage, thus, producing high power d. Various types of solid Li-ion electrolytes have been reported; this review is focused on the most promising solid Li-ion electrolytes based on garnet-type metal oxides. The first studied Li-stuffed garnet-type compds. are Li5La3M2O12 (M = Nb, Ta), which show a Li-ion cond. of ∼10-6 at 25 °C. La and M sites can be substituted by various metal ions leading to Li-rich garnet-type electrolytes, such as Li6ALa2M2O12, (A = Mg, Ca, Sr, Ba, Sr0.5Ba0.5) and Li7La3C2O12 (C = Zr, Sn). Among the known Li-stuffed garnets, Li6.4La3Zr1.4Ta0.6O12 exhibits the highest bulk Li-ion cond. of 10-3 S cm-1 at 25 °C with an activation energy of 0.35 eV, which is an order of magnitude lower than that of the currently used polymer, but is chem. stable at higher temps. and voltages compared to polymer electrolytes. Here, we discuss the chem. compn.-structure-ionic cond. relationship of the Li-stuffed garnet-type oxides, as well as the Li ion conduction mechanism.
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Adams, S.; Rao, R. P. Ion transport and phase transition in Li_7–xLa₃(Zr_2–xM_x)O₁₂ (M = Ta⁵⁺, Nb⁵⁺, x = 0, 0.25). J. Mater. Chem. 2012, 22, 1426– 1434, DOI: 10.1039/C1JM14588F
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49
Ion transport and phase transition in Li7-xLa3(Zr2-xMx)O12 (M = Ta5+, Nb5+, x = 0, 0.25)
Adams, Stefan; Rao, Rayavarapu Prasada
Journal of Materials Chemistry (2012), 22 (4), 1426-1434CODEN: JMACEP; ISSN:0959-9428. (Royal Society of Chemistry)
Due to their favorable combination of high ionic cond. and stability vs. elemental Li, garnet-related Li ion conductors Li7La3Zr2O12 have raised strong interest for both all-solid-state batteries and as protective layers for anode materials. Here we study the correlation between structure and ion mobility in Li7-xLa3(Zr2-xMx)O12 (x = 0, 0.25; M = Ta5+, Nb5+) combining Mol. Dynamics (MD) simulations, bond valence (BV) studies and exptl. characterization. In situ XRD demonstrates a tetragonal-to-cubic phase transition above 450 K for LixLa3Zr2O12. MD simulations using our new BV-based Morse-type force field reproduce static (lattice consts., thermal expansion, phase transition) and dynamic characteristics of this material. Simulations and structure refinements for the tetragonal phase accordingly yield an ordered Li distribution. The majority of Li fully occupies the 16f and 32g octahedral sites. Out of the 2 tetrahedral sites only the 8a site is fully occupied leaving the 16e tetrahedral sites with slightly higher site energy due to the tetragonal distortion vacant. For the cubic phase recent structural studies either suggest a major Li+ redistribution to nearly fully occupied tetrahedral sites and distorted octahedral sites with a low occupancy (which leads to unphys. short Li-Li distances) or suggest the existence of addnl. Li sites. MD simulations however show that the Li distribution just above the phase transition closely resembles that in the tetragonal phase with only slightly more than 1/3 of the now equiv. tetrahedral 24d sites and almost half of the distorted octahedral 96h sites occupied, so that overly short Li-Li distances are avoided. Pentavalent doping enhances ionic cond. by increasing the vacancy concn. and by reducing local Li ordering. At higher temps. Li is gradually redistributed to the tetrahedral sites that can be occupied up to a site occupancy factor of 0.56. BV pathway anal. and closely harmonizing Li trajectories demonstrate that the two partially occupied Li sites of similar site energy form a 3D network suitable for fast ion conduction. The simulated diffusion coeff. and its activation energy closely match the exptl. conductivities. The degree of correlation of the vacancy-type Li+ ion migration is analyzed in terms of the van Hove correlation function.
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Jalem, R.; Rushton, M. J. D.; Manalastas, W., Jr.; Nakayama, M.; Kasuga, T.; Kilner, J. A.; Grimes, R. W. Effects of Gallium Doping in Garnet-Type Li₇La₃Zr₂O₁₂ Solid Electrolytes. Chem. Mater. 2015, 27, 2821– 2831, DOI: 10.1021/cm5045122
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50
Effects of Gallium Doping in Garnet-Type Li7La3Zr2O12 Solid Electrolytes
Jalem, Randy; Rushton, M. J. D.; Manalastas, William; Nakayama, Masanobu; Kasuga, Toshihiro; Kilner, John A.; Grimes, Robin W.
Chemistry of Materials (2015), 27 (8), 2821-2831CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
Garnet-type Li7La3Zr2O12 (LLZrO) is a candidate solid electrolyte material that is now being intensively optimized for application in com. competitive solid state Li+ ion batteries. In this study we investigate, by force-field-based simulations, the effects of Ga3+ doping in LLZrO. We confirm the stabilizing effect of Ga3+ on the cubic phase. We also det. that Ga3+ addn. does not lead to any appreciable structural distortion. Li site connectivity is not significantly deteriorated by the Ga3+ addn. (>90% connectivity retained up to x = 0.30 in Li7-3xGaxLa3Zr2O12). Interestingly, two compositional regions are predicted for bulk Li+ ion cond. in the cubic phase: (i) a decreasing trend for 0 ≤ x ≤ 0.10 and (ii) a relatively flat trend for 0.10 < x ≤ 0.30. This cond. behavior is explained by combining analyses using percolation theory, van Hove space time correlation, the radial distribution function, and trajectory d.
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Deschanvres, A.; Raveau, B.; Sekkal, Z. Mise en evidence et etude cristallographique d’une nouvelle solution solide de type spinelle Li_1+xTi_2–xO₄ 0 ≤ x ≤ 0, 33₃. Mater. Res. Bull. 1971, 6, 699– 704, DOI: 10.1016/0025-5408(71)90103-6
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51
Demonstration and crystallographic study of new spinel-type solid solution Li1+xTi1-3xTi1+2xO4 with O .leq. .tim. .leq. 0.33
Deschanvres, A.; Raveau, B.; Sekkal, Z.
Materials Research Bulletin (1971), 6 (8), 699-704CODEN: MRBUAC; ISSN:0025-5408.
A new solid-soln. spinel type Li1+xTi3+1-3x-Ti4+1+2xO4 with O ≤ x ≤ 0.33 has been isolated. The positions of the different atoms in the cubic cell were detd.
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Ziebarth, B.; Klinsmann, M.; Eckl, T.; Elsasser, C. Lithium diffusion in the spinel phase Li₄Ti₅O₁₂ and in the rocksalt phase Li₇Ti₅O₁₂ of lithium titanate from first principles. Phys. Rev. B 2014, 89, 174301, DOI: 10.1103/PhysRevB.89.174301
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52
Lithium diffusion in the spinel phase Li4Ti5O12 and in the rocksalt phase Li7Ti5O12 of lithium titanate from first principles
Ziebarth, Benedikt; Klinsmann, Markus; Eckl, Thomas; Elsaesser, Christian
Physical Review B: Condensed Matter and Materials Physics (2014), 89 (17), 174301/1-174301/7, 7 pp.CODEN: PRBMDO; ISSN:1098-0121. (American Physical Society)
Lithium titanate (LTO) is a promising candidate as an anode material in future generations of lithium ion batteries due to its high intrinsic safety and stability. In this work, we investigate the diffusion barriers for lithium ions in two different crystal structures of LTO using the d. functional theory. Our calcns. show that the activation barriers vary between 0.30-0.48 eV for the spinel phase Li4Ti5O12 and between 0.20-0.51 eV in the lithiated rocksalt phase Li7Ti5O12. The origins of the rather broad ranges of activation energies are related to different chem. environments of the diffusion channels due to mixed occupancies of some sites in LTO. Our results reveal that the detn. of lithium diffusion consts. in LTO can not be carried out by using a single activation barrier. Instead, the local environment of the diffusion paths must be considered to correctly capture the variety of activation barriers. Moreover, we find the sites which have mixed occupation in LTO to trap lithium vacancies in the spinel phase. This effect is not obsd. in the rocksalt phase. This behavior explains the low lithium diffusivity found in expts. for lithium concns. in the vicinity of the spinel phase.
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Momma, K.; Izumi, F. VESTA: a three-dimensional visualization system for electronic and structural analysis. J. Appl. Crystallogr. 2008, 41, 653– 658, DOI: 10.1107/S0021889808012016
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53
VESTA: a three-dimensional visualization system for electronic and structural analysis
Momma, Koichi; Izumi, Fujio
Journal of Applied Crystallography (2008), 41 (3), 653-658CODEN: JACGAR; ISSN:0021-8898. (International Union of Crystallography)
A cross-platform program, VESTA, has been developed to visualize both structural and volumetric data in multiple windows with tabs. VESTA represents crystal structures by ball-and-stick, space-filling, polyhedral, wire frame, stick, dot-surface and thermal-ellipsoid models. A variety of crystal-chem. information is extractable from fractional coordinates, occupancies and oxidn. states of sites. Volumetric data such as electron and nuclear densities, Patterson functions, and wavefunctions are displayed as isosurfaces, bird's-eye views and two-dimensional maps. Isosurfaces can be colored according to other phys. quantities. Translucent isosurfaces and/or slices can be overlapped with a structural model. Collaboration with external programs enables the user to locate bonds and bond angles in the 'graphics area', simulate powder diffraction patterns, and calc. site potentials and Madelung energies. Electron densities detd. exptl. are convertible into their Laplacians and electronic energy densities.
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Giannozzi, P.; Baroni, S.; Bonini, N.; Calandra, M.; Car, R.; Cavazzoni, C.; Ceresoli, D.; Chiarotti, G. L; Cococcioni, M.; Dabo, I.; Dal Corso, A.; de Gironcoli, S.; Fabris, S.; Fratesi, G.; Gebauer, R.; Gerstmann, U.; Gougoussis, C.; Kokalj, A.; Lazzeri, M.; Martin-Samos, L.; Marzari, N.; Mauri, F.; Mazzarello, R.; Paolini, S.; Pasquarello, A.; Paulatto, L.; Sbraccia, C.; Scandolo, S.; Sclauzero, G.; Seitsonen, A. P; Smogunov, A.; Umari, P.; Wentzcovitch, R. M QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials. J. Phys.: Condens. Matter 2009, 21, 395502, DOI: 10.1088/0953-8984/21/39/395502
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QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials
Giannozzi Paolo; Baroni Stefano; Bonini Nicola; Calandra Matteo; Car Roberto; Cavazzoni Carlo; Ceresoli Davide; Chiarotti Guido L; Cococcioni Matteo; Dabo Ismaila; Dal Corso Andrea; de Gironcoli Stefano; Fabris Stefano; Fratesi Guido; Gebauer Ralph; Gerstmann Uwe; Gougoussis Christos; Kokalj Anton; Lazzeri Michele; Martin-Samos Layla; Marzari Nicola; Mauri Francesco; Mazzarello Riccardo; Paolini Stefano; Pasquarello Alfredo; Paulatto Lorenzo; Sbraccia Carlo; Scandolo Sandro; Sclauzero Gabriele; Seitsonen Ari P; Smogunov Alexander; Umari Paolo; Wentzcovitch Renata M
Journal of physics. Condensed matter : an Institute of Physics journal (2009), 21 (39), 395502 ISSN:.
QUANTUM ESPRESSO is an integrated suite of computer codes for electronic-structure calculations and materials modeling, based on density-functional theory, plane waves, and pseudopotentials (norm-conserving, ultrasoft, and projector-augmented wave). The acronym ESPRESSO stands for opEn Source Package for Research in Electronic Structure, Simulation, and Optimization. It is freely available to researchers around the world under the terms of the GNU General Public License. QUANTUM ESPRESSO builds upon newly-restructured electronic-structure codes that have been developed and tested by some of the original authors of novel electronic-structure algorithms and applied in the last twenty years by some of the leading materials modeling groups worldwide. Innovation and efficiency are still its main focus, with special attention paid to massively parallel architectures, and a great effort being devoted to user friendliness. QUANTUM ESPRESSO is evolving towards a distribution of independent and interoperable codes in the spirit of an open-source project, where researchers active in the field of electronic-structure calculations are encouraged to participate in the project by contributing their own codes or by implementing their own ideas into existing codes.
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Anisimov, V. I.; Zaanen, J.; Andersen, O. K. Band theory and Mott insulators: Hubbard U instead of Stoner I. Phys. Rev. B 1991, 44, 943– 954, DOI: 10.1103/PhysRevB.44.943
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55
Band theory and Mott insulators: Hubbard U instead of Stoner I
Anisimov, V. I.; Zaanen, Jan; Andersen, Ole K.
Physical Review B: Condensed Matter and Materials Physics (1991), 44 (3), 943-54CODEN: PRBMDO; ISSN:0163-1829.
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One of the main challenges of all-solid-state Li-ion batteries is the restricted power d. due to the poor Li-ion transport between the electrodes via the electrolyte. However, to establish what diffusional process is the bottleneck for Li-ion transport requires the ability to distinguish the various processes. The present work investigates the Li-ion diffusion in argyrodite Li6PS5Cl, a promising electrolyte based on its high Li-ion cond., using a combination of 7Li NMR expts. and DFT based mol. dynamics simulations. This allows us to distinguish the local Li-ion mobility from the long-range Li-ion motional process, quantifying both and giving a coherent and consistent picture of the bulk diffusion in Li6PS5Cl. NMR exchange expts. are used to unambiguously characterize Li-ion transport over the solid electrolyte-electrode interface for the electrolyte-electrode combination Li6PS5Cl-Li2S, giving unprecedented and direct quant. insight into the impact of the interface on Li-ion charge transport in all-solid-state batteries. The limited Li-ion transport over the Li6PS5Cl-Li2S interface, orders of magnitude smaller compared with that in the bulk Li6PS5Cl, appears to be the bottleneck for the performance of the Li6PS5Cl-Li2S battery, quantifying one of the major challenges toward improved performance of all-solid-state batteries.
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Groh, M. F.; Sullivan, M. J.; Gaultois, M. W.; Pecher, O.; Griffith, K. J.; Grey, C. P. Interface Instability in LiFePO₄-Li_3+xP_1-xSi_xO₄ All-Solid-State Batteries. Chem. Mater. 2018, 30, 5886– 5895, DOI: 10.1021/acs.chemmater.8b01746
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Interface Instability in LiFePO4-Li3+xP1-xSixO4 All-Solid-State Batteries
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Chemistry of Materials (2018), 30 (17), 5886-5895CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
All-solid-state batteries based on noncombustible solid electrolytes are promising candidates for safe and high energy storage systems, but it remains a challenge to prep. systems with stable interfaces between the various solid components that survive both the synthesis conditions and electrochem. cycling. The cathode mixts. based on carbon-coated LiFePO4 active material and Li3+xP1-xSixO4 solid electrolyte are investigated for potential use in all-solid-state batteries. Half-cells were constructed by combining both compds. into pellets by spark plasma sintering (SPS). The fast and quant. formation is reported of two solid solns. (LiFePO4-Fe2SiO4 and Li3PO4-Li2FeSiO4) for different compns. and ratios of the pristine compds., as tracked by powder X-ray diffraction and solid-state NMR; X-ray absorption near-edge spectroscopy confirms the formation of iron silicates similar to Fe2SiO4. SEM and energy dispersive X-ray spectroscopy reveal diffusion of iron cations up to 40 μm into the solid electrolyte even in the short processing times accessible by SPS. Electrochem. cycling of the SPS-treated cathode mixts. demonstrates a substantial decrease in capacity following the formation of the solid solns. during sintering. Consequently, all-solid-state batteries based on LiFePO4 and Li3+xP1-xSixO4 would necessitate iron ion blocking layers. More generally, this study highlights the importance of systematic studies on the fundamental reactions at the active material-solid electrolyte interfaces to enable the introduction of protective layers for com. successful all-solid-state batteries.
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Figure 1
Figure 1. Surfaces of (a) LiCoO₂ (LCO)-(104), (b) LCO-(110), (c) β-Li₃PS₄ (LPS)-(010), (d) γ-L₃PO₄ (LPO)-(001), (e) Li₇La₃Zr₂O₁₂ (LLZO)-(001), and (f) Li₄Ti₅O₁₂(LTO)-(111), examined in this work. Li, O, P, S, Co, La, Zr, and Ti are depicted as light green, red, purple, yellow, blue, brown, blue, and light blue spheres, respectively. CoO₆, PS₄, PO₄, ZrO₆, LaO₈, and TiO₆ complexes are represented by blue, green, gray, light green, brown, and light blue polyhedrons, respectively.
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Figure 2
Figure 2. Calculated interface structures with the lowest energies of (a) LCO(104)/LPS(010) and (b) LCO(110)/LPS(010). The insets show the detailed atomic structures at the interface. CoO₆ and PS₄ complexes are represented by blue and green polyhedrons.
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Figure 3
Figure 3. PDOS of the calculated lowest energy interface of LCO(104)/LPS(010). Red line: total DOS; green line: LCO atoms; blue line: LPS atoms; brown line: LCO atoms facing the vacuum; light blue line: the first LCO layer facing the LPS slab. We set zero reference energy as the center of the band gap. LCO vac and LCO 1st correspond to the LCO layer facing the vacuum and the interface with LPS, respectively.
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Figure 4
Figure 4. Distributions of Li sites classified with the Li vacancy-formation energies at the (a) LCO(104)/LPS(010) and (b) both LCO/LPS interfaces, respectively. The vacancy-formation energies of 65 Li sites in 8 different interface structures (23 sites in three different interface structures) are calculated for LCO(104)/LPS(010) and (LCO(110)/LPS(010)). The distributions are normalized by the total number of calculated Li sites. The blue bars denote the distribution of all the calculated Li sites in the LCO/LPS and the red bars denote those of calculated Li sites located in the LPS region.
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Figure 5
Figure 5. (a) Representative LCO(104)/LPS(010) interface structure with the site labels and the mutual cation exchange energies for (b) Co ↔ P and (c) Co ↔ Li.
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Figure 6
Figure 6. Optimized interface structures of (a) LCO(104)/LPO(010) and (b) LCO(104)/LPO(001). The insets show the detailed atomic structures at the interface. CoO₆ and PO₄ complexes are represented by blue and gray polyhedrons.
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Figure 7
Figure 7. PDOS of the optimized interfaces of LCO(104)/LPO(001). Red line: total DOS; green line: PDOS from LCO atoms; blue line: PDOS from LPO atoms; brown line: PDOS from LCO atoms facing the vacuum; light blue line: PDOS from first LCO layer facing the LPO slab. We set zero reference energy as the band gap center.
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Figure 8
Figure 8. Distributions of Li sites divided by their Li vacancy-formation energies at the (a) LCO(104)/LPO(010) and (b) LCO(104))/LPO(001) interfaces. The vacancy-formation energies of 28 Li sites in four different interface structures and 36 sites in five different interface structures are calculated for LCO(104)/LPO(010) and LCO(104)/LPO(001), respectively. The distributions are normalized by the total number of calculated Li sites. The blue bar graphs denote the distribution of all the calculated Li sites in LCO/LPO, and the red bar graphs denote those of the calculated Li sites located in the LPO region.
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Figure 9
Figure 9. (a) Schematic picture of the optimized LCO(104)/LPO(001) interface with the sites where we calculated mutual cation exchange energy. (b) Co ↔ P and (c) Co ↔ Li cation exchange energies corresponding to sites denoted in (a).
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Figure 10
Figure 10. Optimized interface structures of LCO(104)/LLZO(001). The insets show the detailed atomic structures at the interface. CoO₆, ZrO₆, and LaO₈ complexes are represented by dark blue, light green, and brown polyhedrons.
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Figure 11
Figure 11. PDOS of the optimized interfaces of LCO(104)/LLZO(001). Red line: total DOS; green line: LCO atoms; blue line: LLZO atoms; violet line: LCO atoms facing the vacuum; light blue line: the first LCO layer facing the LLZO slab. We set zero reference energy as the center of the band gap.
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Figure 12
Figure 12. Distributions of the Li sites classified by their Li vacancy-formation energies at the LCO(104)/LLZO(001) interface. The vacancy-formation energies of 36 Li sites in four different interface structures are calculated. The distributions are normalized by the total number of calculated Li sites. The blue bar graphs denote the distribution of all the calculated Li sites in LCO/LLZO, and the red bar graphs denote those of the calculated Li sites located in the LLZO region.
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Figure 13
Figure 13. (a) Structure of the LCO(104)/LLZO(001) interface (upper panel) and its corresponding (b) Co ↔ Zr and (c) Co ↔ La mutual cation exchange reaction energies (lower panel). The positive values of exchange energies indicate endothermic reactions.
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Figure 14
Figure 14. Optimized interface structures of LTO(111)/LPS(010). The insets show the detailed atomic structures at the interface. TiO₆ and PS₄ complexes are represented by light blue and green polyhedrons.
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Figure 15
Figure 15. PDOS of the optimized interfaces of LTO(111)/LPS(010). Red line: total DOS; gray line: LTO atoms; blue line: LPS atoms. We set zero reference energy as the center of the band gap.
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Figure 16
Figure 16. Distributions of Li sites divided by their Li vacancy-formation energies at the LTO(111)/LPS(010) interface. The vacancy-formation energies of 31 Li sites in four different interface structures are calculated. The distributions are normalized by the total number of calculated Li sites. The blue bar graphs denote the distribution of all the calculated Li sites in LTO/LPS, and the red bar graphs denote those of calculated Li sites located in the LPS region.
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  A review. Lithium batteries are characterized by high specific energy, high efficiency and long life. These unique properties have made lithium batteries the power sources of choice for the consumer electronics market with a prodn. of the order of billions of units per yr. These batteries are also expected to find a prominent role as ideal electrochem. storage systems in renewable energy plants, as well as power systems for sustainable vehicles, such as hybrid and elec. vehicles. However, scaling up the lithium battery technol. for these applications is still problematic since issues such as safety, costs, wide operational temp. and materials availability, are still to be resolved. This review focuses first on the present status of lithium battery technol., then on its near future development and finally it examines important new directions aimed at achieving quantum jumps in energy and power content.
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5. 5
  Masquelier, C. Lithium ions on the fast track. Nat. Mater. 2011, 10, 649– 650, DOI: 10.1038/nmat3105
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  Solid electrolytes: Lithium ions on the fast track
  Masquelier, Christian
  Nature Materials (2011), 10 (9), 649-650CODEN: NMAACR; ISSN:1476-1122. (Nature Publishing Group)
  A review. Solvent-based electrolytes used at present in Li-ion batteries can be unsafe for large-scale applications. A cryst. electrolyte with high ionic cond. could soon enable all-solid energy storage systems.
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6. 6
  Takada, K. Progress and Prospective of Solid-State Lithium Batteries. Acta Mater. 2013, 61, 759– 770, DOI: 10.1016/j.actamat.2012.10.034
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  Progress and prospective of solid-state lithium batteries
  Takada, Kazunori
  Acta Materialia (2013), 61 (3), 759-770CODEN: ACMAFD; ISSN:1359-6454. (Elsevier Ltd.)
  A review. The development of lithium-ion batteries has energized studies of solid-state batteries, because the non-flammability of their solid electrolytes offers a fundamental soln. to safety concerns. Since poor ionic conduction in solid electrolytes is a major drawback in solid-state batteries, such studies were focused on the enhancement of ionic cond. The studies have identified some high performance solid electrolytes; however, some disadvantages have remained hidden until their use in batteries. This paper reviews the development of solid electrolytes and their application to solid-state lithium batteries.
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7. 7
  Kamaya, N.; Homma, K.; Yamakawa, Y.; Hirayama, M.; Kanno, R.; Yonemura, M.; Kamiyama, T.; Kato, Y.; Hama, S.; Kawamoto, K.; Mitsui, A. A lithium superionic conductor. Nat. Mater. 2011, 10, 682– 686, DOI: 10.1038/nmat3066
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  7
  A lithium superionic conductor
  Kamaya, Noriaki; Homma, Kenji; Yamakawa, Yuichiro; Hirayama, Masaaki; Kanno, Ryoji; Yonemura, Masao; Kamiyama, Takashi; Kato, Yuki; Hama, Shigenori; Kawamoto, Koji; Mitsui, Akio
  Nature Materials (2011), 10 (9), 682-686CODEN: NMAACR; ISSN:1476-1122. (Nature Publishing Group)
  Batteries are a key technol. in modern society. They are used to power elec. and hybrid elec. vehicles and to store wind and solar energy in smart grids. Electrochem. devices with high energy and power densities can currently be powered only by batteries with org. liq. electrolytes. However, such batteries require relatively stringent safety precautions, making large-scale systems complicated and expensive. The application of solid electrolytes is currently limited because they attain practically useful conductivities (10-2 S/cm) only at 50-80°, which is one order of magnitude lower than those of org. liq. electrolytes. Here, the authors report a Li superionic conductor, Li10GeP2S12 that has a new 3-dimensional framework structure. It exhibits an extremely high Li ionic cond. of 12 mS/cm at room temp. This represents the highest cond. achieved in a solid electrolyte, exceeding even those of liq. org. electrolytes. This new solid-state battery electrolyte has many advantages in terms of device fabrication (facile shaping, patterning and integration), stability (non-volatile), safety (non-explosive) and excellent electrochem. properties (high cond. and wide potential window).
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8. 8
  Kato, Y.; Hori, S.; Saito, T.; Suzuki, K.; Hirayama, M.; Mitsui, A.; Yonemura, M.; Iba, H.; Kanno, R. High-power all-solid-state batteries using sulfide superionic conductors. Nat. Energy 2016, 1, 16030, DOI: 10.1038/nenergy.2016.30
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  High-power all-solid-state batteries using sulfide superionic conductors
  Kato, Yuki; Hori, Satoshi; Saito, Toshiya; Suzuki, Kota; Hirayama, Masaaki; Mitsui, Akio; Yonemura, Masao; Iba, Hideki; Kanno, Ryoji
  Nature Energy (2016), 1 (4), 16030CODEN: NEANFD; ISSN:2058-7546. (Nature Publishing Group)
  Compared with Li-ion batteries with liq. electrolytes, all-solid-state batteries offer an attractive option owing to their potential in improving the safety and achieving both high power and high energy densities. Despite extensive research efforts, the development of all-solid-state batteries still falls short of expectation largely because of the lack of suitable candidate materials for the electrolyte required for practical applications. Here the authors report Li superionic conductors with an exceptionally high cond. (25 mS cm-1 for Li9.54Si1.74P1.44S11.7Cl0.3), as well as high stability ( ∼0 V vs. Li metal for Li9.6P3S12). A fabricated all-solid-state cell based on this Li conductor has very small internal resistance, esp. at 100 oC. The cell possesses high specific power that is superior to that of conventional cells with liq. electrolytes. Stable cycling with a high c.d. of 18 C (charging/discharging in just 3 min; where C is the C-rate) is also demonstrated.
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9. 9
  Murugan, R.; Thangadurai, V.; Weppner, W. Fast Lithium Ion Conduction in Garnet-Type Li₇La₃Zr₂O₁₂. Angew. Chem., Int. Ed. 2007, 46, 7778– 7781, DOI: 10.1002/anie.200701144
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  9
  Fast lithium ion conduction in garnet-type Li7La3Zr2O12
  Murugan, Ramaswamy; Thangadurai, Venkataraman; Weppner, Werner
  Angewandte Chemie, International Edition (2007), 46 (41), 7778-7781CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
  Low activation energy and fast Li ion conduction were obsd. for the new compd., Li7La3Zr2O12. Relative to previously reported Li garnets, this solid electrolyte shows a larger cubic lattice const., higher Li ion concn., lower degree of chem. interaction between the Li+ and the other lattice constituents, and higher densification.
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10. 10
  Inaguma, Y.; Liquan, C.; Itoh, M.; Nakamura, T.; Uchida, T.; Ikuta, H.; Wakihara, M. High ionic conductivity in lithium lanthanum titanate. Solid State Commun. 1993, 86, 689– 693, DOI: 10.1016/0038-1098(93)90841-A
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  10
  High ionic conductivity in lithium lanthanum titanate
  Inaguma, Yoshiyuki; Chen, Liquan; Itoh, Mitsuru; Nakamura, Tetsuro; Uchida, Takashi; Ikuta, Hiromasa; Wakihara, Masataka
  Solid State Communications (1993), 86 (10), 689-93CODEN: SSCOA4; ISSN:0038-1098.
  The polycryst. Li0.34(1)La0.51(1)TiO2.94(2) shows high ionic cond. >2 × 10-5 cm-1 (d.c. method) at room temp., which is compared with that of Li3.5V0.5Ge0.5O4. This compd. has cubic perovskite structure whose cell parameter is 3.8710(2) Å. By a.c. impedance anal., the equiv. circuit of the sample could be divided into 2 parts; bulk crystal and grain boundary. The ionic cond. of the bulk part is as high as 1 × 10-3 S cm-1 at room temp. Such a high cond. is considered to be attributed to the presence of a lot of equiv. sites for Li ion to occupy and freely move in this perovskite. This compd. is easy to react with Li metal and the electronic cond. has become much higher than before being in contact with Li. It can be explained that Ti ion was reduced by Li insertion into a vacant site and then an electron carrier was introduced.
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11. 11
  Takada, K.; Ohta, N.; Zhang, L.; Fukuda, K.; Sakaguchi, L.; Ma, R.; Osada, M.; Sasaki, T. Interfacial modification for high-power solid-state lithium batteries. Solid State Ionics 2008, 179, 1333– 1337, DOI: 10.1016/j.ssi.2008.02.017
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  Interfacial modification for high-power solid-state lithium batteries
  Takada, Kazunori; Ohta, Narumi; Zhang, Lianqi; Fukuda, Katsutoshi; Sakaguchi, Isao; Ma, Renzhi; Osada, Minoru; Sasaki, Takayoshi
  Solid State Ionics (2008), 179 (27-32), 1333-1337CODEN: SSIOD3; ISSN:0167-2738. (Elsevier B.V.)
  Interfaces between LiCoO2 and sulfide solid electrolytes were modified in order to enhance the high-rate capability of solid-state lithium batteries. Thin films of oxide solid electrolytes, Li4Ti5O12, LiNbO3, and LiTaO3, were interposed at the interfaces as buffer layers. Changes in the high-rate performance upon heat treatment revealed that the buffer layer should be formed at low temp. to avoid thermal diffusion of the elements. Buffer layers of LiNbO3 and LiTaO3 can be formed at low temp. for the interfacial modification, because they show high ionic conduction in their amorphous states, and so are more effective than Li4Ti5O12 for high-power densities.
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12. 12
  Ohta, N.; Takada, K.; Zhang, L.; Ma, R.; Osada, M.; Sasaki, T. Enhancement of the high-rate capability of solid-state lithium batteries by nanoscale interfacial modification. Adv. Mater. 2006, 18, 2226– 2229, DOI: 10.1002/adma.200502604
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  12
  Enhancement of the high-rate capability of solid-state lithium batteries by nanoscale interfacial modification
  Ohta, Narumi; Takada, Kazunori; Zhang, Lianqi; Ma, Renzhi; Osada, Minoru; Sasaki, Takayoshi
  Advanced Materials (Weinheim, Germany) (2006), 18 (17), 2226-2229CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)
  The high-rate capability of solid-state rechargeable Li batteries with sulfide electrolytes improved when the LiCoO2 particles are spray-coated with Li4Ti5O12. The power densities of the solid-state battery with the coated LiCoO2 are comparable to those of com. Li-ion batteries.
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13. 13
  Ohta, N.; Takada, K.; Sakaguchi, I.; Zhang, L.; Ma, R.; Fukuda, K.; Osada, M.; Sasaki, T. LiNbO₃-coated LiCoO₂ as cathode material for all solid-state lithium secondary batteries. Electrochem. Commun. 2007, 9, 1486– 1490, DOI: 10.1016/j.elecom.2007.02.008
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  13
  LiNbO3-coated LiCoO2 as cathode material for all solid-state lithium secondary batteries
  Ohta, Narumi; Takada, Kazunori; Sakaguchi, Isao; Zhang, Lianqi; Ma, Renzhi; Fukuda, Katsutoshi; Osada, Minoru; Sasaki, Takayoshi
  Electrochemistry Communications (2007), 9 (7), 1486-1490CODEN: ECCMF9; ISSN:1388-2481. (Elsevier B.V.)
  The enhancement of the high-rate capabilities for solid-state Li secondary batteries is reported. A nanometer thick LiNbO3 layer was interposed between LiCoO2 and the solid sulfide electrolyte as buffer layer. This decreased the interfacial resistance in the cathode and enhanced the high-rate capabilities of the batteries - this can enable design of Li secondary batteries free from safety issues.
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14. 14
  Sakuda, A.; Kitaura, H.; Hayashi, A.; Tadanaga, K.; Tatsumisago, M. Modification of Interface Between LiCoO₂ Electrode and Li₂S – P₂S₅ Solid Electrolyte Using Li₂O – SiO₂ Glassy Layers. J. Electrochem. Soc. 2009, 156, A27– A32, DOI: 10.1149/1.3005972
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  14
  Modification of Interface Between LiCoO2 Electrode and Li2S-P2S5 Solid Electrolyte Using Li2O-SiO2 Glassy Layers
  Sakuda, Atsushi; Kitaura, Hirokazu; Hayashi, Akitoshi; Tadanaga, Kiyoharu; Tatsumisago, Masahiro
  Journal of the Electrochemical Society (2009), 156 (1), A27-A32CODEN: JESOAN; ISSN:0013-4651. (Electrochemical Society)
  Effects of modification of the electrode/electrolyte interface with Li2O-SiO2 thin films on impedance profiles and rate capabilities of all-solid-state In/80Li2S·20P2S5 glass ceramic/LiCoO2 cells were studied. Large resistance was obsd. at the LiCoO2-electrode/sulfide-electrolyte interface in all-solid-state cells. The interfacial resistance was decreased by 0.06% oxide coatings on LiCoO2; the effective coatings were a Li-ion conductive Li2SiO3 glassy film and an insulative SiO2 film. The Li2SiO3 coating film decreased the interfacial resistance more effectively when the coating amts. increased from 0.06 to 0.6% (film thickness was ∼10 nm). However, 0.6% of SiO2 coating exhibited higher interfacial resistance than non-coating because the thick SiO2 coating film acted as a high-resistance layer. Temp. dependence of the interfacial resistance suggests that the resistance decrease was achieved mainly by an increase of pre-exponential factor rather than by a decrease of activation energy for ion conduction at the interface. At room temp., all-solid-state cells with Li2SiO3-coated LiCoO2 were discharged even under the high c.d. of 6.4 mA/cm2.
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15. 15
  Yamada, H.; Oga, Y.; Saruwatari, I.; Moriguchi, I. Local Structure and Ionic Conduction at Interfaces of Electrode and Solid Electrolytes. J. Electrochem. Soc. 2012, 159, A380– A385, DOI: 10.1149/2.035204jes
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  15
  Local structure and ionic conduction at interfaces of electrode and solid electrolytes
  Yamada, Hirotsohi; Oga, Yusuke; Saruwatari, Isamu; Moriguchi, Isamu
  Journal of the Electrochemical Society (2012), 159 (4), A380-A385CODEN: JESOAN; ISSN:0013-4651. (Electrochemical Society)
  All solid state batteries are attracting interests as next generation energy storage devices. However, little is known about interfaces between active materials and solid electrolytes, which may affect performance of the devices. Interfacial phenomena between electrodes and solid electrolytes of all solid state batteries were studied by using nanocomposites of Li2SiO3-TiO2, Li2SiO3-LiTiO2, and Li2SiO3-FePO4. Studies on ionic cond. of these composites revealed Li ion transfer across the interfaces without elec. field, which depended on electrode potentials. For Li2SiO3-TiO2, cond. of the composites was enhanced by addn. of TiO2 and well explained by space charge layer model. With LiTiO2 which shows lower electrode potential, the cond. was deteriorated due to decrease in vacancies in Li2SiO3. At the interface of Li2SiO3-FePO4, a lot of Li ions in Li2SiO3 are trapped at the interface or maybe are inserted into FePO4, resulting in many vacancies in Li2SiO3 and lattice distortion. The results show the ionic conduction at the interface is strongly affected by the electrode potential and the importance of design of interfaces of all solid state batteries is pointed out.
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16. 16
  Takada, K. Interfacial Nanoarchitectonics for Solid-State Lithium Batteries. Langmuir 2013, 29, 7538– 7541, DOI: 10.1021/la3045253
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  16
  Interfacial Nanoarchitectonics for Solid-State Lithium Batteries
  Takada, Kazunori
  Langmuir (2013), 29 (24), 7538-7541CODEN: LANGD5; ISSN:0743-7463. (American Chemical Society)
  A review of interfacial structures in lithium batteries that lower the interfacial resistance to enable high-power interfaces by controlling the carrier d. Strong demand for solid-state Li batteries has prompted intensive research for achieving fast ionic conduction in solids. Although the highest cond. found among sulfides is higher than that of liq. electrolytes, it improves the battery performance only in combination with electrodes via a low-resistance interface.
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17. 17
  Takada, K.; Ohta, N.; Zhang, L.; Xu, X.; Hang, B. T.; Ohnishi, T.; Osada, M.; Sasaki, T. Interfacial phenomena in solid-state lithium battery with sulfide solid electrolyte. Solid State Ionics 2012, 225, 594– 597, DOI: 10.1016/j.ssi.2012.01.009
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  17
  Interfacial phenomena in solid-state lithium battery with sulfide solid electrolyte
  Takada, Kazunori; Ohta, Narumi; Zhang, Lianqi; Xu, Xiaoxiong; Hang, Bui Thi; Ohnishi, Tsuyoshi; Osada, Minoru; Sasaki, Takayoshi
  Solid State Ionics (2012), 225 (), 594-597CODEN: SSIOD3; ISSN:0167-2738. (Elsevier B.V.)
  The effects of surface coating on electrode properties of LiMn2O4 in a sulfide solid electrolyte were investigated. The surface coating with LiNbO3 reduced the electrode resistance by two orders of magnitude. Changes in the electrode properties were very similar to those obsd. for the corresponding LiCoO2 electrodes, which strongly suggest that the space-charge layer formed at the high-voltage cathode/sulfide electrolyte interface is rate-detg. and must be controlled to improve the rate capability.
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18. 18
  Sakuda, A.; Hayashi, A.; Tatsumisago, M. Interfacial Observation between LiCoO₂ Electrode and Li₂S–P₂S₅ Solid Electrolytes of All-Solid-State Lithium Secondary Batteries Using Transmission Electron Microscopy. Chem. Mater. 2010, 22, 949– 956, DOI: 10.1021/cm901819c
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  18
  Interfacial Observation between LiCoO2 Electrode and Li2S-P2S5 Solid Electrolytes of All-Solid-State Lithium Secondary Batteries using Transmission Electron Microscopy
  Sakuda, Atsushi; Hayashi, Akitoshi; Tatsumisago, Masahiro
  Chemistry of Materials (2010), 22 (3), 949-956CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
  In all-solid-state lithium secondary batteries, both the electrode and electrolyte materials are solid. The electrode and solid electrolyte interface structure and morphol. affect a battery electrochem. performance. Observation of the interface between LiCoO2 cathode and highly lithium-ion-conducting Li2S-P2S5 solid electrolyte was conducted using transmission electron microscopy. An interfacial layer was formed at the interface between LiCoO2 electrode and Li2S-P2S5 solid electrolyte after the battery initial charge. Furthermore, mutual diffusions of Co, P, and S at the interface between LiCoO2 and Li2S-P2S5 were obsd. The mutual diffusion and the formation of the interfacial layer were suppressed using LiCoO2 particles coated with Li2SiO3 thin film. Results showed that all-solid-state batteries using Li2SiO3-coated LiCoO2 had better electrochem. performance than those using non-coated LiCoO2. The all-solid-state batteries functioned at -30°. Moreover, the all-solid-state battery using Li2SiO3-coated LiCoO2 was charged and discharged under a high c.d. of 40 mA/cm2 at 100°.
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19. 19
  Ohtomo, T.; Hayashi, A.; Tatsumisago, M.; Tsuchida, Y.; Hama, S.; Kawamoto, K. All-solid-state lithium secondary batteries using the 75Li₂S·25P₂S₅ glass and the 70Li₂S·30P₂S₅ glass–ceramic as solid electrolytes. J. Power Sources 2013, 233, 231– 235, DOI: 10.1016/j.jpowsour.2013.01.090
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  19
  All-solid-state lithium secondary batteries using the 75Li2S·25P2S5 glass and the 70Li2S·30P2S5 glass-ceramic as solid electrolytes
  Ohtomo, Takamasa; Hayashi, Akitoshi; Tatsumisago, Masahiro; Tsuchida, Yasushi; Hama, Shigenori; Kawamoto, Koji
  Journal of Power Sources (2013), 233 (), 231-235CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)
  The 70Li2S·30P2S5 glass-ceramic showed high ion cond. of 1.5 × 10-3 S cm-1 at room temp. The 75Li2S·25P2S5 glass showed ion cond. of 5.0 × 10-4 S cm-1 at room temp. and high chem. stability. All-solid-state C/LiCoO2 cells using those materials as solid electrolytes were assembled. Their cell performance were compared. The cell using the 70Li2S·30P2S5 glass-ceramic showed superior rate performance to the cell using the 75Li2S·25P2S5 glass. On the other hand, the cell using the 75Li2S·25P2S5 glass showed superior cycle performance to the cell using the 70Li2S·30P2S5 glass-ceramic. It was suggested that solid electrolytes in all-solid-state batteries preferably had both high ion cond. and high chem. stability.
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20. 20
  Woo, H. J.; Trevey, J. E.; Cavanagh, A. S.; Choi, Y. S.; Kim, S. C.; George, S. M.; Oh, K. H.; Lee, S. H. Nanoscale Interface Modification of LiCoO₂ by Al₂O₃ Atomic Layer Deposition for Solid-State Li Batteries. J. Electrochem. Soc. 2012, 159, A1120– A1124, DOI: 10.1149/2.085207jes
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  20
  Nanoscale interface modification of LiCoO2 by Al2O3 atomic layer deposition for solid-state Li batteries
  Woo, Jae Ha; Trevey, James E.; Cavanagh, Andrew S.; Choi, Yong Seok; Kim, Seul Cham; George, Steven M.; Oh, Kyu Hwan; Lee, Se-Hee
  Journal of the Electrochemical Society (2012), 159 (7), A1120-A1124CODEN: JESOAN; ISSN:0013-4651. (Electrochemical Society)
  Cycle stability of solid-state lithium batteries (SSLBs) using a LiCoO2 cathode is improved by at. layer deposition (ALD) on active material powder with Al2O3. SSLBs with LiCoO2/Li3.15Ge0.15P0.85S4/77.5Li2S-22.5P2S5/Li structure were constructed and tested by charge-discharge cycling at a c.d. of 45 μA cm-2 with a voltage window of 3.3 ∼ 4.3 V (vs. Li/Li+). Capacity degrdn. during cycling is suppressed dramatically by employing Al2O3 ALD-coated LiCoO2 in the composite cathode. Whereas only 70% of capacity retention is achieved for uncoated LiCoO2 after 25 cycles, 90% of capacity retention is obsd. for LiCoO2 with ALD Al2O3 layers. Electrochem. impedance spectroscopy (EIS) and transmission electron microscopy (TEM) studies show that the presence of ALD Al2O3 layers on the surface of LiCoO2 reduces interfacial resistance development between LiCoO2 and solid state electrolyte (SSE) during cycling.
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21. 21
  Haruyama, J.; Sodeyama, K.; Han, L.; Takada, K.; Tateyama, Y. Space–Charge Layer Effect at Interface between Oxide Cathode and Sulfide Electrolyte in All-Solid-State Lithium-Ion Battery. Chem. Mater. 2014, 26, 4248– 4255, DOI: 10.1021/cm5016959
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  21
  Space-Charge Layer Effect at Interface between Oxide Cathode and Sulfide Electrolyte in All-Solid-State Lithium-Ion Battery
  Haruyama, Jun; Sodeyama, Keitaro; Han, Liyuan; Takada, Kazunori; Tateyama, Yoshitaka
  Chemistry of Materials (2014), 26 (14), 4248-4255CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
  The authors theor. elucidated the characteristics of the space-charge layer (SCL) at interfaces between oxide cathode and sulfide electrolyte in all-solid-state Li-ion batteries (ASS-LIBs) and the effect of the buffer layer interposition, for the 1st time, via the calcns. with d. functional theory (DFT) + U framework. As a most representative system, the authors examd. the interfaces between LiCoO2 cathode and β-Li3PS4 solid electrolyte (LCO/LPS), and the LiCoO2/LiNbO3/β-Li3PS4 (LCO/LNO/LPS) interfaces with the LiNbO3 buffer layers. The DFT+U calcns., coupling with a systematic procedure for interface matching, showed the stable structures and the electronic states of the interfaces. The LCO/LPS interface has attractive Li adsorption sites and rather disordered structure, whereas the interposition of the LNO buffer layers forms smooth interfaces without Li adsorption sites for both LCO and LPS sides. The calcd. energies of the Li-vacancy formation and the Li migration reveal that subsurface Li in the LPS side can begin to transfer at the under-voltage condition in the LCO/LPS interface, which suggests the SCL growth at the beginning of charging, leading to the interfacial resistance. The LNO interposition suppresses this growth of SCL and provides smooth Li transport paths free from the possible bottlenecks. These aspects on the at. scale will give a useful perspective for the further improvement of the ASS-LIB performance.
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22. 22
  Haruyama, J.; Sodeyama, K.; Tateyama, Y. Cation Mixing Properties toward Co Diffusion at the LiCoO₂ Cathode/Sulfide Electrolyte Interface in a Solid-State Battery. ACS Appl. Mater. Interfaces 2017, 9, 286– 292, DOI: 10.1021/acsami.6b08435
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  22
  Cation Mixing Properties toward Co Diffusion at the LiCoO2 Cathode/Sulfide Electrolyte Interface in a Solid-State Battery
  Haruyama, Jun; Sodeyama, Keitaro; Tateyama, Yoshitaka
  ACS Applied Materials & Interfaces (2017), 9 (1), 286-292CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
  All-solid-state Li-ion batteries (ASS-LIBs) are expected to be the next-generation battery, however, their large interfacial resistance hinders their widespread application. To understand and resolve the possible causes of this resistance, we examd. mutual diffusion properties of the cation elements at LiCoO2 (LCO) cathode/β-Li3PS4 (LPS) solid electrolyte interface as a representative system as well as the effect of a LiNbO3 buffer layer by first-principles calcns. Evaluating energies of exchanging ions between the cathode and the electrolyte, we found that the mixing of Co and P is energetically preferable to the unmixed states at the LCO/LPS interface. We also demonstrated that the interposition of the buffer layer suppresses such mixing because the exchange of Co and Nb is energetically unfavorable. Detailed analyses of the defect levels and the exchange energies by using the individual bulk crystals as well as the interfaces suggest that the lower interfacial states in the energy gap can make a major contribution to the stabilization of the Co - P exchange, although the anion bonding preference of Co and P as well as the electrostatic interactions may have effects as well. Finally, the Co - P exchanges induce interfacial Li sites with low chem. potentials, which enhance the growth of the Li depletion layer. These atomistic understandings can be meaningful for the development of ASS-LIBs with smaller interfacial resistances.
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23. 23
  Tateyama, Y.; Gao, B.; Jalem, R.; Haruyama, J. Theoretical picture of positive electrode–solid electrolyte interface in all-solid-state battery from electrochemistry and semiconductor physics viewpoints. Curr. Opin. Electrochem. 2019, 17, 149– 157, DOI: 10.1016/j.coelec.2019.06.003
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  23
  Theoretical picture of positive electrode-solid electrolyte interface in all-solid-state battery from electrochemistry and semiconductor physics viewpoints
  Tateyama, Yoshitaka; Gao, Bo; Jalem, Randy; Haruyama, Jun
  Current Opinion in Electrochemistry (2019), 17 (), 149-157CODEN: COEUCY; ISSN:2451-9111. (Elsevier B.V.)
  All-solid-state battery has attracted significant attention as a promising next-generation energy storage. However, interfacial resistance of ion transport between the pos. electrode and solid electrolyte is still a crucial issue for the all-solid-state battery commercialization. Although some mechanisms such as space charge layer and reaction layer effects have been suggested, the ionic and electronic behaviors at the solid-solid interfaces have not yet been fully elucidated. Here, we address theor. microscopic understanding of the interfacial ionics and electronics from the viewpoints of electrochem. and semiconductor physics, in conjunction with the results of recent d. functional theory calcns.
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24. 24
  Gao, B.; Jalem, R.; Ma, Y.; Tateyama, Y. Li⁺ Transport Mechanism at the Heterogeneous Cathode/Solid Electrolyte Interface in an All-Solid-State Battery via the First-Principles Structure Prediction Scheme. Chem. Mater. 2020, 32, 85– 96, DOI: 10.1021/acs.chemmater.9b02311
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  24
  Li+ Transport Mechanism at the Heterogeneous Cathode/Solid Electrolyte Interface in an All-Solid-State Battery via the First-Principles Structure Prediction Scheme
  Gao, Bo; Jalem, Randy; Ma, Yanming; Tateyama, Yoshitaka
  Chemistry of Materials (2020), 32 (1), 85-96CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
  High interfacial resistance between a cathode and solid electrolyte (SE) has been a long-standing problem for all-solid-state batteries (ASSBs). Though thermodn. approaches suggested possible phase transformations at the interfaces, direct analyses of the ionic and electronic states at the solid/solid interfaces are still crucial. Here, newly constructed scheme is used for predicting heterogeneous interface structures via the swarm-intelligence-based crystal structure anal. by particle swarm optimization method, combined with d. functional theory calcns., and systematically investigated the mechanism of Li-ion (Li+) transport at the interface in LiCoO2 cathode/β-Li3PS4 SE, a representative ASSB system. The sampled favorable interface structures indicate that the interfacial reaction layer is formed with both mixing of Co and P cations and mixing of O and S anions. The calcd. site-dependent Li chem. potentials μLi(r) and potential energy surfaces for Li+ migration across the interfaces reveal that interfacial Li+ sites with higher μLi(r) values cause dynamic Li+ depletion with the interfacial electron transfer in the initial stage of charging. The Li+-depleted space can allow oxidative decompn. of SE materials. These pieces of evidence theor. confirm the primary origin of the obsd. interfacial resistance in ASSBs and the mechanism of the resistance decrease obsd. with oxide buffer layers (e.g., LiNbO3) and oxide SE. The present study also provides a perspective for the structure sampling of disordered heterogeneous solid/solid interfaces on the at. scale.
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25. 25
  Haruta, M.; Shiraki, S.; Suzuki, T.; Kumatani, A.; Ohsawa, T.; Takagi, Y.; Shimizu, R.; Hitosugi, T. Negligible “Negative Space-Charge Layer Effects” at Oxide-Electrolyte/Electrode Interfaces of Thin-Film Batteries. Nano Lett. 2015, 15, 1498– 1502, DOI: 10.1021/nl5035896
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  25
  Negligible "Negative Space-Charge Layer Effects" at Oxide-Electrolyte/Electrode Interfaces of Thin-Film Batteries
  Haruta, Masakazu; Shiraki, Susumu; Suzuki, Tohru; Kumatani, Akichika; Ohsawa, Takeo; Takagi, Yoshitaka; Shimizu, Ryota; Hitosugi, Taro
  Nano Letters (2015), 15 (3), 1498-1502CODEN: NALEFD; ISSN:1530-6984. (American Chemical Society)
  In this paper, the surprisingly low electrolyte/electrode interface resistance of 8.6 Ω cm2 obsd. in thin-film batteries is reported. This value is an order of magnitude smaller than that presented in previous reports on all-solid-state lithium batteries. The value is also smaller than that found in a liq. electrolyte-based batteries. The low interface resistance indicates that the neg. space-charge layer effects at the Li3PO4-xNx/LiCoO2 interface are negligible and demonstrates that it is possible to fabricate all-solid state batteries with faster charging/discharging properties.
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26. 26
  Kawasoko, H.; Shiraki, S.; Suzuki, T.; Shimizu, R.; Hitosugi, T. Extremely Low Resistance of Li₃PO₄ Electrolyte/Li(Ni_0.5Mn_1.5)O₄ Electrode Interfaces. ACS Appl. Mater. Interfaces 2018, 10, 27498– 27502, DOI: 10.1021/acsami.8b08506
  [ACS Full Text ], [CAS], Google Scholar
  26
  Extremely Low Resistance of Li3PO4 Electrolyte/Li(Ni0.5Mn1.5)O4 Electrode Interfaces
  Kawasoko, Hideyuki; Shiraki, Susumu; Suzuki, Toru; Shimizu, Ryota; Hitosugi, Taro
  ACS Applied Materials & Interfaces (2018), 10 (32), 27498-27502CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
  Solid-state Li batteries contg. Li(Ni0.5Mn1.5)O4 as a 5 V-class pos. electrode are expected to revolutionize mobile devices and elec. vehicles. However, practical applications of such batteries are hampered by the high resistance at their solid electrolyte/electrode interfaces. Here, an extremely low electrolyte/electrode interface resistance of 7.6 Ω cm2 is achieved in solid-state Li batteries with Li(Ni0.5Mn1.5)O4. Furthermore, spontaneous migration is obsd. of Li ions from the solid electrolyte to the pos. electrode after the formation of the electrolyte/electrode interface. Finally, stable fast charging and discharging is demonstrated of the solid-state Li batteries at a c.d. of 14 mA/cm2. These results provide a solid foundation to understand and fabricate low-resistance electrolyte/electrode interfaces.
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27. 27
  Sharafi, A.; Kazyak, E.; Davis, A. L.; Yu, S.; Thompson, T.; Siegel, D. J.; Dasgupta, N. P.; Sakamoto, J. Surface Chemistry Mechanism of Ultra-Low Interfacial Resistance in the Solid-State Electrolyte Li₇La₃Zr₂O₁₂. Chem. Mater. 2017, 29, 7961– 7968, DOI: 10.1021/acs.chemmater.7b03002
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  27
  Surface Chemistry Mechanism of Ultra-Low Interfacial Resistance in the Solid-State Electrolyte Li7La3Zr2O12
  Sharafi, Asma; Kazyak, Eric; Davis, Andrew L.; Yu, Seungho; Thompson, Travis; Siegel, Donald J.; Dasgupta, Neil P.; Sakamoto, Jeff
  Chemistry of Materials (2017), 29 (18), 7961-7968CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
  The impact of surface chem. on the interfacial resistance between the Li7La3Zr2O12 (LLZO) solid-state electrolyte and a metallic Li electrode is revealed. Control of surface chem. allows the interfacial resistance to be reduced to 2 Ω cm2, lower than that of liq. electrolytes, without the need for interlayer coatings. A mechanistic understanding of the origins of ultra-low resistance is provided by quant. evaluating the linkages between interfacial chem., Li wettability, and electrochem. phenomena. A combination of Li contact angle measurements, XPS, first-principles calcns., and impedance spectroscopy demonstrates that the presence of common LLZO surface contaminants, Li2CO3 and LiOH, result in poor wettability by Li and high interfacial resistance. On the basis of this mechanism, a simple procedure for removing these surface layers is demonstrated, which results in a dramatic increase in Li wetting and the elimination of nearly all interfacial resistance. The low interfacial resistance is maintained over one-hundred cycles and suggests a straightforward pathway to achieving high energy and power d. solid-state batteries.
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28. 28
  Zhu, Y.; He, X.; Mo, Y. Origin of Outstanding Stability in the Lithium Solid Electrolyte Materials: Insights from Thermodynamic Analyses Based on First-Principles Calculations. ACS Appl. Mater. Interfaces 2015, 7, 23685– 23693, DOI: 10.1021/acsami.5b07517
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  28
  Origin of Outstanding Stability in the Lithium Solid Electrolyte Materials: Insights from Thermodynamic Analyses Based on First-Principles Calculations
  Zhu, Yizhou; He, Xingfeng; Mo, Yifei
  ACS Applied Materials & Interfaces (2015), 7 (42), 23685-23693CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
  First-principles calcns. were performed to investigate the electrochem. stability of lithium solid electrolyte materials in all-solid-state Li-ion batteries. The common solid electrolytes were found to have a limited electrochem. window. The results suggest that the outstanding stability of the solid electrolyte materials is not thermodynamically intrinsic but is originated from kinetic stabilizations. The sluggish kinetics of the decompn. reactions cause a high overpotential leading to a nominally wide electrochem. window obsd. in many expts. The decompn. products, similar to the solid-electrolyte-interphases, mitigate the extreme chem. potential from the electrodes and protect the solid electrolyte from further decompns. With the aid of the first-principles calcns., the passivation mechanism is revealed of these decompn. interphases and quantified the extensions of the electrochem. window from the interphases. It was also found that the artificial coating layers applied at the solid electrolyte and electrode interfaces have a similar effect of passivating the solid electrolyte. The newly gained understanding provided general principles for developing solid electrolyte materials with enhanced stability and for engineering interfaces in all-solid-state Li-ion batteries.
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29. 29
  Zhu, Y.; He, X.; Mo, Y. First principles study on electrochemical and chemical stability of solid electrolyte–electrode interfaces in all-solid-state Li-ion batteries. J. Mater. Chem. A 2016, 4, 3253– 3266, DOI: 10.1039/C5TA08574H
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  29
  First principles study on electrochemical and chemical stability of solid electrolyte-electrode interfaces in all-solid-state Li-ion batteries
  Zhu, Yizhou; He, Xingfeng; Mo, Yifei
  Journal of Materials Chemistry A: Materials for Energy and Sustainability (2016), 4 (9), 3253-3266CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)
  All-solid-state Li-ion batteries based on ceramic solid electrolyte materials are a promising next-generation energy storage technol. with high energy d. and enhanced cycle life. The poor interfacial conductance is one of the key limitations in enabling all-solid-state Li-ion batteries. However, the origin of this poor conductance has not been understood, and there is limited knowledge about the solid electrolyte-electrode interfaces in all-solid-state Li-ion batteries. In this study, we performed first principles calcns. to evaluate the thermodn. of the interfaces between solid electrolyte and electrode materials and to identify the chem. and electrochem. stabilities of these interfaces. Our computation results reveal that many solid electrolyte-electrode interfaces have limited chem. and electrochem. stability, and that the formation of interphase layers is thermodynamically favorable at these interfaces. These formed interphase layers with different properties significantly affect the electrochem. performance of all-solid-state Li-ion batteries. The mechanisms of applying interfacial coating layers to stabilize the interface and to reduce interfacial resistance are illustrated by our computation. This study demonstrates a computational scheme to evaluate the chem. and electrochem. stability of heterogeneous solid interfaces. The enhanced understanding of the interfacial phenomena provides the strategies of interface engineering to improve performances of all-solid-state Li-ion batteries.
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30. 30
  Richards, W. D.; Miara, L. J.; Wang, Y.; Kim, J. C.; Ceder, G. Interface Stability in Solid-State Batteries. Chem. Mater. 2016, 28, 266– 273, DOI: 10.1021/acs.chemmater.5b04082
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  30
  Interface Stability in Solid-State Batteries
  Richards, William D.; Miara, Lincoln J.; Wang, Yan; Kim, Jae Chul; Ceder, Gerbrand
  Chemistry of Materials (2016), 28 (1), 266-273CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
  Development of high cond. solid-state electrolytes for lithium ion batteries has proceeded rapidly in recent years, but incorporating these new materials into high-performing batteries has proven difficult. Interfacial resistance is now the limiting factor in many systems, but the exact mechanisms of this resistance have not been fully explained - in part because exptl. evaluation of the interface can be very difficult. In this work, we develop a computational methodol. to examine the thermodn. of formation of resistive interfacial phases. The predicted interfacial phase formation is well correlated with exptl. interfacial observations and battery performance. We calc. that thiophosphate electrolytes have esp. high reactivity with high voltage cathodes and a narrow electrochem. stability window. We also find that a no. of known electrolytes are not inherently stable but react in situ with the electrode to form passivating but ionically conducting barrier layers. As a ref. for experimentalists, we tabulate the stability and expected decompn. products for a wide range of electrolyte, coating, and electrode materials including a no. of high-performing combinations that have not yet been attempted exptl.
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31. 31
  Deng, Z.; Zhu, Z.; Chu, L.-H.; Ong, S.-P. Data-Driven First-Principles Methods for the Study and Design of Alkali Superionic Conductors. Chem. Mater. 2017, 29, 281– 288, DOI: 10.1021/acs.chemmater.6b02648
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  31
  Data-Driven First-Principles Methods for the Study and Design of Alkali Superionic Conductors
  Deng, Zhi; Zhu, Zhuoying; Chu, Iek-Heng; Ong, Shyue Ping
  Chemistry of Materials (2017), 29 (1), 281-288CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
  A detailed exposition of how first-principles methods can be used to guide alkali superionic conductor (ASIC) study and design is presented. Using the argyrodite Li6PS5Cl as a case study, it is demonstrated how modern information technol. (IT) infrastructure and software tools can facilitate the assessment of alkali superionic conductors in terms of various crit. properties of interest such as phase and electrochem. stability and ionic cond. The emphasis is on well-documented, reproducible anal. code that can be readily generalized to other material systems and design problems. For our chosen Li6PS5Cl case study material, it is shown that Li excess is crucial to enhancing its cond. by increasing the occupancy of interstitial sites that promote long-range Li+ diffusion between cage-like frameworks. The predicted room-temp. conductivities and activation barriers are in reasonably good agreement with exptl. values.
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32. 32
  Miara, L. J.; Richards, W. D.; Wang, Y. E.; Ceder, G. First-Principles Studies on Cation Dopants and Electrolyte|Cathode Interphases for Lithium Garnets. Chem. Mater. 2015, 27, 4040– 4047, DOI: 10.1021/acs.chemmater.5b01023
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  32
  First-Principles Studies on Cation Dopants and Electrolyte|Cathode Interphases for Lithium Garnets
  Miara, Lincoln J.; Richards, William Davidson; Wang, Yan E.; Ceder, Gerbrand
  Chemistry of Materials (2015), 27 (11), 4040-4047CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
  Lithium garnet with the formula Li7La3Zr2O12 (LLZO) has many properties of an ideal electrolyte in all-solid state lithium batteries. However, internal resistance in batteries utilizing these electrolytes remains high. For widespread adoption, the LLZO's internal resistance must be lowered by increasing its bulk cond., reducing grain boundary resistance, and/or pairing it with an appropriate cathode to minimize interfacial resistance. Cation doping has been shown to be crucial in LLZO to stabilize the higher cond. cubic structure, yet there is still little understanding about which cations have high soly. in LLZO. In this work, d. functional theory (DFT) is used to calc. the defect energies and site preference of all possible dopants in these materials. The findings suggest several novel dopants such as Zn2+ and Mg2+ predicted to be stable on the Li- and Zr-sites, resp. To understand the source of interfacial resistance between the electrolyte and the cathode, the thermodn. stability is investigated of the electrolyte|cathode interphase, calcg. the reaction energy for LLMO (M = Zr, Ta) against LiCoO2, LiMnO2, and LiFePO4 (LCO, LMO, and LFP, resp.) cathodes over the voltage range seen in lithium-ion battery operation. The results suggest that, for LLZO, the LLZO|LCO is the most stable, showing only a low driving force for decompn. in the charged state into La2O3, La2Zr2O7, and Li2CoO3, while the LLZO|LFP appears to be the most reactive, forming Li3PO4, La2Zr2O7, LaFeO3, and Fe2O3. These results provide a ref. for use by researchers interested in bonding these electrolytes to cathodes.
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33. 33
  Tang, H.; Deng, Z.; Lin, Z.; Wang, Z.; Chu, I.-H.; Chen, C.; Zhu, Z.; Zheng, C.; Ong, S. P. Probing Solid–Solid Interfacial Reactions in All-Solid-State Sodium-Ion Batteries with First-Principles Calculations. Chem. Mater. 2018, 30, 163– 173, DOI: 10.1021/acs.chemmater.7b04096
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  33
  Probing Solid-Solid Interfacial Reactions in All-Solid-State Sodium-Ion Batteries with First-Principles Calculations
  Tang, Hanmei; Deng, Zhi; Lin, Zhuonan; Wang, Zhenbin; Chu, Iek-Heng; Chen, Chi; Zhu, Zhuoying; Zheng, Chen; Ong, Shyue Ping
  Chemistry of Materials (2018), 30 (1), 163-173CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
  We present an exposition of first-principles approaches to elucidating interfacial reactions in all-solid-state sodium-ion batteries. We will demonstrate how thermodn. approxns. based on assumptions of fast alkali diffusion and multispecies equil. can be used to effectively screen combinations of Na-ion electrodes, solid electrolytes, and buffer oxides for electrochem. and chem. compatibility. We find that exchange reactions, esp. between simple oxides and thiophosphate groups to form PO43-, are the main cause of large driving forces for cathode/solid electrolyte interfacial reactions. A high reactivity with large vol. changes is also predicted at the Na anode/solid electrolyte interface, while the Na2Ti3O7 anode is predicted to be much more stable against a broad range of solid electrolytes. We identify several promising binary oxides, Sc2O3, SiO2, TiO2, ZrO2, and HfO2, that are similarly or more chem. compatible with most electrodes and solid electrolytes than the commonly used Al2O3 is. Finally, we show that ab initio mol. dynamics simulations of the NaCoO2/Na3PS4 interface model predict that the formation of SO42--contg. compds. and Na3P is kinetically favored over the formation of PO43--contg. compds., in contrast to the predictions of the thermodn. models. This work provides useful insights into materials selection strategies for enabling stable electrode/solid electrolyte interfaces, a crit. bottleneck in designing all-solid-state sodium-ion batteries, and outlines several testable predictions for future exptl. validation.
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34. 34
  Du, Y. A.; Holzwarth, N. A. W. Mechanisms of Li⁺ diffusion in crystalline γ^– and β–Li₃PO₄ electrolytes from first principles. Phys. Rev. B 2007, 76, 174302, DOI: 10.1103/PhysRevB.76.174302
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  34
  Mechanisms of Li+ diffusion in crystalline γ- and β-Li3PO4 electrolytes from first principles
  Du, Yaojun A.; Holzwarth, N. A. W.
  Physical Review B: Condensed Matter and Materials Physics (2007), 76 (17), 174302/1-174302/14CODEN: PRBMDO; ISSN:1098-0121. (American Physical Society)
  Recently, there was significant interest in developing solid-state lithium ion electrolytes for use in batteries and related technologies. The authors used 1st-principles modeling techniques based on d.-functional theory and the nudged elastic band method to examine possible Li ion diffusion mechanisms in idealized crystals of the electrolyte material Li3PO4 in both the γ and β cryst. forms, considering both vacancy and interstitial processes to find the migration energies Em. Interstitial diffusion via an interstitialcy mechanism involving the concerted motion of an interstitial Li ion and a neighboring lattice Li ion may provide the most efficient ion transport in Li3PO4. Ion transport in undoped crystals depends on the formation of vacancy-interstitial pairs requiring an addnl. energy Ef, which results in a thermal activation energy EA = Em + Ef/2. The calcd. values of EA are in excellent agreement with single crystal measurements on γ-Li3PO4. The results examine the similarities and differences between the diffusion processes in the γ and β crystal structures. The authors analyze the zone center phonon modes in both crystals to further validate the calcns. with exptl. measurements and to det. the range of vibrational frequencies assocd. with Li ion motions which might contribute to the diffusion processes.
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35. 35
  Leung, K. DFT modelling of explicit solid–solid interfaces in batteries: methods and challenges. Phys. Chem. Chem. Phys. 2020, 22, 10412– 10425, DOI: 10.1039/C9CP06485K
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  DFT modelling of explicit solid-solid interfaces in batteries: methods and challenges
  Leung, Kevin
  Physical Chemistry Chemical Physics (2020), 22 (19), 10412-10425CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)
  D. Functional Theory (DFT) calcns. of electrode material properties in high energy d. storage devices like lithium batteries have been std. practice for decades. In contrast, DFT modeling of explicit interfaces in batteries arguably lacks universally adopted methodol. and needs further conceptual development. In this paper, we focus on solid-solid interfaces, which are ubiquitous not just in all-solid state batteries; liq.-electrolyte-based batteries often rely on thin, solid passivating films on electrode surfaces to function. We use metal anode calcns. to illustrate that explicit interface models are crit. for elucidating contact potentials, elec. fields at interfaces, and kinetic stability with respect to parasitic reactions. The examples emphasize three key challenges: (1) the "dirty" nature of most battery electrode surfaces; (2) voltage calibration and control; and (3) the fact that interfacial structures are governed by kinetics, not thermodn. To meet these challenges, developing new computational techniques and importing insights from other electrochem. disciplines will be beneficial.
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36. 36
  Sumita, M.; Tanaka, Y.; Ikeda, M.; Ohno, T. Charged and Discharged States of Cathode/Sulfide Electrolyte Interfaces in All-Solid-State Lithium Ion Batteries. J. Phys. Chem. C 2016, 120, 13332– 13339, DOI: 10.1021/acs.jpcc.6b01207
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  36
  Charged and Discharged States of Cathode/Sulfide Electrolyte Interfaces in All-Solid-State Lithium Ion Batteries
  Sumita, Masato; Tanaka, Yoshinori; Ikeda, Minoru; Ohno, Takahisa
  Journal of Physical Chemistry C (2016), 120 (25), 13332-13339CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)
  Interfaces between cathodes and sulfide electrolytes exhibit high resistance in all-solid-state lithium ion batteries. In this paper, to elucidate the origin of the high interface resistance we have theor. investigated the properties of the cathode interfaces with the sulfide electrolyte and oxide electrolyte for comparison. From the d. functional mol. dynamics simulations of the LiFePO4/Li3PS4 interface in both discharged and charged states, we have demonstrated the instability of the sulfide interface in the charged state, i.e., the lithium depletion and oxidn. on the sulfide side near the interface, in contrast to the oxide interfaces. The obtained results imply the formation of a Li-depleted layer around the sulfide interfaces during charging and support the validity of the insertion of oxide buffer layers at the interface to reduce the interface resistance.
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37. 37
  Kramer, D.; Ceder, G. Tailoring the Morphology of LiCoO₂: A First Principles Study. Chem. Mater. 2009, 21, 3799– 3809, DOI: 10.1021/cm9008943
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  37
  Tailoring the Morphology of LiCoO2: A First Principles Study
  Kramer, Denis; Ceder, Gerbrand
  Chemistry of Materials (2009), 21 (16), 3799-3809CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
  Surface energies of several low-index surfaces of layered LiCoO2 were studied as a function of the external Li and O chem. potentials by First Principles calcns. in the generalized gradient approxn. (GGA) to d. functional theory (DFT), treating on-site electron correlation within the DFT+U framework. The set of surfaces contained in the equil. shape depended on the environment. The (0001) and (10‾14) surfaces were present for all reasonable values of the Li and O chem. potentials. The (01‾12) surface, however, is stable only under oxidizing conditions. The equil. shape is sensitive to the equilibration environment because the thermodynamically favorable surface terminations and surface energies of the polar (0001) and (01‾12) surfaces are a function of the environment. This provides a lever to tailor the crystal shape according to application requirements (e.g., as active material in Li-ion batteries).
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38. 38
  Shao-Horn, Y.; Croguennec, L.; Delmas, C.; Nelson, E. C.; O’keefe, M. A. Atomic resolution of lithium ions in LiCoO₂. Nat. Mater. 2003, 2, 464– 467, DOI: 10.1038/nmat922
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  Atomic resolution of lithium ions in LiCoO2
  Shao-Horn Yang; Croguennec Laurence; Delmas Claude; Nelson E Chris; O'Keefe Michael A
  Nature materials (2003), 2 (7), 464-7 ISSN:1476-1122.
  LiCoO2 is the most common lithium storage material for lithium rechargeable batteries, used widely to power portable electronic devices such as laptop computers. Operation of lithium rechargeable batteries is dependent on reversible lithium insertion and extraction processes into and from the host materials of lithium storage. Ordering of lithium and vacancies has a profound effect on the physical properties of the host materials and the electrochemical performance of lithium batteries. However, probing lithium ions has been difficult when using traditional X-ray and neutron powder diffraction techniques due to lithium's relatively low scattering power when compared with those of oxygen and transition metals. In the work presented here, we have succeeded in simultaneously resolving columns of cobalt, oxygen and lithium atoms in layered LiCoO2 battery material, using experimental focal series of LiCoO2 images obtained at sub-angstrom resolution in a mid-voltage transmission electron microscope. Lithium atoms are the smallest and lightest metal atoms, and scatter electrons only very weakly. We believe our observations of lithium to be the first by electron microscopy, and that they show promise for direct visualization of the ordering of lithium and vacancies in transition metal oxides.
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39. 39
  Daheron, L.; Martinez, H.; Dedryvere, R.; Baraille, I.; Menetrier, M.; Denage, C.; Delmas, C.; Gonbeau, D. Surface Properties of LiCoO₂ Investigated by XPS Analyses and Theoretical Calculations. J. Phys. Chem. C 2009, 113, 5843– 5852, DOI: 10.1021/jp803266w
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  Surface Properties of LiCoO2 Investigated by XPS Analyses and Theoretical Calculations
  Daheron, L.; Martinez, H.; Dedryvere, R.; Baraille, I.; Menetrier, M.; Denage, C.; Delmas, C.; Gonbeau, D.
  Journal of Physical Chemistry C (2009), 113 (14), 5843-5852CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)
  XPS analyses (core peaks and valence spectra), under highly controlled conditions, have been carried out on stoichiometric LiCoO2 and lithium-overstoichiometric Li1+yCo1-yO2-y (y ∼ 0.05) materials, with significant changes obsd. in the oxygen peaks. Indeed, beside the component attributed to the O2- anions of the cryst. network, a second one with variable intensity has been obsd. on the high binding energy side. With the support of ab initio biperiodical calcns. on LiCoO2, we propose that this peculiar oxygen signature is partially assocd., for LiCoO2, to undercoordinated oxygen atoms coming from (0 0 1) oriented surfaces. These surface oxygen anions are significantly less neg. than the ones of the lattice. These results, in conjunction with SEM analyses for the lithium overstoichiometric material (as prepd. and thermally treated), show that the presence of defects (oxygen vacancies) has to also be considered in the overstoichiometric case. As in battery material, all reactions (the intercalation but also the parasitic ones) occur through the surface; characterization of its crystallog. nature (as well as its electronic properties) is a key point to a better understanding and optimization of Li ion batteries.
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40. 40
  Van der Ven, A.; Ceder, G.; Asta, M.; Tepesch, P. D. First-principles theory of ionic diffusion with nondilute carriers. Phys. Rev. B: Condens. Matter Mater. Phys. 2001, 64, 184307, DOI: 10.1103/PhysRevB.64.184307
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  First-principles theory of ionic diffusion with nondilute carriers
  Van der Ven, A.; Ceder, G.; Asta, M.; Tepesch, P. D.
  Physical Review B: Condensed Matter and Materials Physics (2001), 64 (18), 184307/1-184307/17CODEN: PRBMDO; ISSN:0163-1829. (American Physical Society)
  Many multicomponent materials exhibit significant configurational disorder. Diffusing ions in such materials migrate along a network of sites that have different energies and that are sepd. by configuration dependent activation barriers. We describe a formalism that enables a first-principles calcn. of the diffusion coeff. in solids exhibiting configurational disorder. The formalism involves the implementation of a local cluster expansion to describe the configuration dependence of activation barriers. The local cluster expansion serves as a link between accurate first-principles calcns. of the activation barriers and kinetic Monte Carlo simulations. By introducing a kinetically resolved activation barrier, we show that a cluster expansion for the thermodn. of ionic disorder can be combined with a local cluster expansion to obtain the activation barrier for migration in any configuration. This ensures that in kinetic Monte Carlo simulations, detailed balance is maintained at all times and kinetic quantities can be calcd. in a properly equilibrated thermodn. state. As an example, we apply this formalism for an investigation of lithium diffusion in LixCoO2. A study of the activation barriers in LixCoOx within the local d. approxn. shows that the migration mechanism and activation barriers depend strongly on the local lithium-vacancy arrangement around the migrating lithium ion. By parameterizing the activation barriers with a local cluster expansion and applying it in kinetic Monte Carlo simulations, we predict that lithium diffusion in layered LixCoO2 is mediated by divacancies at all lithium concns. Furthermore, due to a strong concn. dependence of the activation barrier, the predicted diffusion coeff. varies by several orders of magnitude with lithium concn. x.
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41. 41
  Liu, Z.; Fu, W.; Payzant, E. A.; Yu, X.; Wu, Z.; Dudney, N. J.; Kiggans, J.; Hong, K.; Rondinone, A. J.; Liang, C. Anomalous High Ionic Conductivity of Nanoporous β-Li₃PS₄. J. Am. Chem. Soc. 2013, 135, 975– 978, DOI: 10.1021/ja3110895
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  Anomalous High Ionic Conductivity of Nanoporous β-Li3PS4
  Liu, Zengcai; Fu, Wujun; Payzant, E. Andrew; Yu, Xiang; Wu, Zili; Dudney, Nancy J.; Kiggans, Jim; Hong, Kunlun; Rondinone, Adam J.; Liang, Chengdu
  Journal of the American Chemical Society (2013), 135 (3), 975-978CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
  Lithium-ion-conducting solid electrolytes hold promise for enabling high-energy battery chemistries and circumventing safety issues of conventional lithium batteries. Achieving the combination of high ionic cond. and a broad electrochem. window in solid electrolytes is a grand challenge for the synthesis of battery materials. Herein we show an enhancement of the room-temp. lithium-ion cond. by 3 orders of magnitude through the creation of nanostructured Li3PS4. This material has a wide electrochem. window (5 V) and superior chem. stability against lithium metal. The nanoporous structure of Li3PS4 reconciles two vital effects that enhance the ionic cond.: (a) the redn. of the dimensions to a nanometer-sized framework stabilizes the high-conduction β phase that occurs at elevated temps., and (b) the high surface-to-bulk ratio of nanoporous β-Li3PS4 promotes surface conduction. Manipulating the ionic cond. of solid electrolytes has far-reaching implications for materials design and synthesis in a broad range of applications, including batteries, fuel cells, sensors, photovoltaic systems, and so forth.
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42. 42
  Maruyama, M.; Kanno, R.; Kawamoto, Y.; Kamiyama, T. Structure of the thio-LISICON, Li₄GeS₄. Solid State Ionics 2002, 154–155, 789– 794, DOI: 10.1016/S0167-2738(02)00492-7
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  Zemann, J. Die Kristallstruktur von Lithiumphosphat, Li₃PO₄. Acta Crystallogr. 1960, 13, 863– 867, DOI: 10.1107/S0365110X60002132
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  The crystal structure of lithium phosphate, Li3PO4
  Zemann, J.
  Acta Crystallographica (1960), 13 (), 863-7CODEN: ACCRA9; ISSN:0365-110X.
  The crystal structure of orthorhombic Li3PO4 was detd. and carefully refined in the projections parallel to the 2 shortest axes. The important features of the at. arrangement are PO4 groups which are linked together by Li ions in tetrahedral co.ovrddot.ordination.
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44. 44
  Bates, J. B.; Dudney, N. J.; Gruzalski, G. R.; Zuhr, R. A.; Choudhury, A.; Luck, D. F.; Robertson, J. D. Electrical properties of amorphous lithium electrolyte thin films. Solid State Ionics 1992, 53–56, 647– 654, DOI: 10.1016/0167-2738(92)90442-R
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  Electrical properties of amorphous lithium electrolyte thin films
  Bates, J. B.; Dudney, N. J.; Gruzalski, G. R.; Zuhr, R. A.; Choudhury, A.; Luck, C. F.; Robertson, J. D.
  Solid State Ionics (1992), 53-56 (Pt. 1), 647-54CODEN: SSIOD3; ISSN:0167-2738.
  The impedance of xLi2O-ySiO2·zP2O5 thin films deposited by RF-magnetron sputtering was analyzed using two models in which the frequency dependence of the bulk response was represented by: (1) a Cole-Cole dielec. function and (2) a const. phase angle element. Increases in the cond. with Li2O concn. and with addn. of SiO2 to Li2O-P2O5 compns. are attributed to an increase in Li+ mobility caused by changes in the film structure. A new amorphous oxynitride electrolyte, Li3.3PO3.9N0.17, prepd. by sputtering Li3PO4 in N2, has a cond. at 25° of 2 × 10-6 S/cm and is stable in contact with lithium.
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45. 45
  Bates, J. B.; Dudney, N. J.; Gruzalski, G. R.; Zuhr, R. A.; Choudhury, A.; Luck, D. F.; Robertson, J. D. Fabrication and characterization of amorphous lithium electrolyte thin films and rechargeable thin-film batteries. J. Power Sources 1993, 43, 103– 110, DOI: 10.1016/0378-7753(93)80106-Y
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  Fabrication and characterization of amorphous lithium electrolyte thin films and rechargeable thin-film batteries
  Bates, J. B.; Dudney, N. J.; Gruzalski, G. R.; Zuhr, R. A.; Choudhury, A.; Luck, C. F.; Robertson, J. D.
  Journal of Power Sources (1993), 43 (1-3), 103-10CODEN: JPSODZ; ISSN:0378-7753.
  Amorphous Li oxide and oxynitride thin films were synthesized by radio-frequency magnetron sputtering of Li silicates and Li phosphates in Ar, Ar + O, Ar + N, or N. The compn., structure, and elec. properties of the films were detd. using ion and electron beam, x-ray, optical, photoelectron, and a.c. impedance techniques. For Li phosphosilicate films, ion cond. ≤1.4 × 10-6 S/cm at 25° was obsd., but none of the films were stable in contact with Li. A thin-film Li P oxynitride electrolyte prepd. by sputtering Li3PO4 in pure N had cond. of 2 × 10-6 S/cm at 25° and excellent long-term stability in contact with Li. Thin-film cells of 1-μm-thick amorphous V2O5 cathode, 1-μm-thick oxynitride electrolyte film, and 5-μm-thick Li anode were cycled between 3.7 and 1.5 V at discharge rate of ≤100 μA/cm2 and charge rate of ≤20 μA/cm2. The open-circuit voltage of 3.6-3.7 V of fully-charged cells remained virtually unchanged after months of storage.
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  Ivanov-Shitz, A. K.; Kireev, V. V.; Mel’nikov, O. K.; Demianets, L. N. Growth and ionic conductivity of γ-Li₃PO₄. Crystallogr. Rep. 2001, 46, 864– 867, DOI: 10.1134/1.1405880
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  Du, Y. A.; Holzwarth, N. A. W. Li Ion Diffusion Mechanisms in the Crystalline Electrolyte γ-Li₃PO₄. J. Electrochem. Soc. 2007, 154, A999– A1004, DOI: 10.1149/1.2772200
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  Li ion diffusion mechanisms in the crystalline electrolyte γ-Li3PO4
  Du, Yaojun A.; Holzwarth, N. A. W.
  Journal of the Electrochemical Society (2007), 154 (11), A999-A1004CODEN: JESOAN; ISSN:0013-4651. (Electrochemical Society)
  Solid state Li-ion electrolytes are important in batteries and related technologies. The authors used 1st-principles modeling techniques based on DFT and the nudged elastic band method to examine Li ion diffusion mechanisms in idealized crystals of the electrolyte material, Li3PO4. In modeling the Li-ion vacancy diffusion, the authors find direct hopping between neighboring metastable vacancy configurations to have a minimal migration barrier of Em = 0.6 eV. In modeling the Li-ion interstitial diffusion, the authors find an interstices-related mechanism, involving the concerted motion of an interstitial Li-ion and a neighboring Li ion of the host lattice, that can result in a migration barrier as low as Em = 0.2 eV. The minimal formation energy of a Li-ion vacancy-interstitial pair is Ef = 1.6 eV. Assuming the activation energy for intrinsic defects to be given by EA = Em + Ef/2, the calcns. find EA = 1.0-1.2 eV for ionic diffusion in cryst. γ-Li3PO4, in agreement with exptl. values of 1.1-1.3 eV.
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48. 48
  Thangadurai, V.; Narayanan, S.; Pinzaru, D. Garnet-type solid-state fast Li ion conductors for Li batteries: critical review. Chem. Soc. Rev. 2014, 43, 4714– 4727, DOI: 10.1039/c4cs00020j
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  Garnet-type solid-state fast Li ion conductors for Li batteries: critical review
  Thangadurai, Venkataraman; Narayanan, Sumaletha; Pinzaru, Dana
  Chemical Society Reviews (2014), 43 (13), 4714-4727CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)
  A review. Batteries are electrochem. devices that store elec. energy in the form of chem. energy. Among known batteries, Li ion batteries (LiBs) provide the highest gravimetric and volumetric energy densities, making them ideal candidates for use in portable electronics and plug-in hybrid and elec. vehicles. Conventional LiBs use an org. polymer electrolyte, which exhibits several safety issues including leakage, poor chem. stability and flammability. The use of a solid-state (ceramic) electrolyte to produce all-solid-state LiBs can overcome all of the above issues. Also, solid-state Li batteries can operate at high voltage, thus, producing high power d. Various types of solid Li-ion electrolytes have been reported; this review is focused on the most promising solid Li-ion electrolytes based on garnet-type metal oxides. The first studied Li-stuffed garnet-type compds. are Li5La3M2O12 (M = Nb, Ta), which show a Li-ion cond. of ∼10-6 at 25 °C. La and M sites can be substituted by various metal ions leading to Li-rich garnet-type electrolytes, such as Li6ALa2M2O12, (A = Mg, Ca, Sr, Ba, Sr0.5Ba0.5) and Li7La3C2O12 (C = Zr, Sn). Among the known Li-stuffed garnets, Li6.4La3Zr1.4Ta0.6O12 exhibits the highest bulk Li-ion cond. of 10-3 S cm-1 at 25 °C with an activation energy of 0.35 eV, which is an order of magnitude lower than that of the currently used polymer, but is chem. stable at higher temps. and voltages compared to polymer electrolytes. Here, we discuss the chem. compn.-structure-ionic cond. relationship of the Li-stuffed garnet-type oxides, as well as the Li ion conduction mechanism.
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49. 49
  Adams, S.; Rao, R. P. Ion transport and phase transition in Li_7–xLa₃(Zr_2–xM_x)O₁₂ (M = Ta⁵⁺, Nb⁵⁺, x = 0, 0.25). J. Mater. Chem. 2012, 22, 1426– 1434, DOI: 10.1039/C1JM14588F
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  Ion transport and phase transition in Li7-xLa3(Zr2-xMx)O12 (M = Ta5+, Nb5+, x = 0, 0.25)
  Adams, Stefan; Rao, Rayavarapu Prasada
  Journal of Materials Chemistry (2012), 22 (4), 1426-1434CODEN: JMACEP; ISSN:0959-9428. (Royal Society of Chemistry)
  Due to their favorable combination of high ionic cond. and stability vs. elemental Li, garnet-related Li ion conductors Li7La3Zr2O12 have raised strong interest for both all-solid-state batteries and as protective layers for anode materials. Here we study the correlation between structure and ion mobility in Li7-xLa3(Zr2-xMx)O12 (x = 0, 0.25; M = Ta5+, Nb5+) combining Mol. Dynamics (MD) simulations, bond valence (BV) studies and exptl. characterization. In situ XRD demonstrates a tetragonal-to-cubic phase transition above 450 K for LixLa3Zr2O12. MD simulations using our new BV-based Morse-type force field reproduce static (lattice consts., thermal expansion, phase transition) and dynamic characteristics of this material. Simulations and structure refinements for the tetragonal phase accordingly yield an ordered Li distribution. The majority of Li fully occupies the 16f and 32g octahedral sites. Out of the 2 tetrahedral sites only the 8a site is fully occupied leaving the 16e tetrahedral sites with slightly higher site energy due to the tetragonal distortion vacant. For the cubic phase recent structural studies either suggest a major Li+ redistribution to nearly fully occupied tetrahedral sites and distorted octahedral sites with a low occupancy (which leads to unphys. short Li-Li distances) or suggest the existence of addnl. Li sites. MD simulations however show that the Li distribution just above the phase transition closely resembles that in the tetragonal phase with only slightly more than 1/3 of the now equiv. tetrahedral 24d sites and almost half of the distorted octahedral 96h sites occupied, so that overly short Li-Li distances are avoided. Pentavalent doping enhances ionic cond. by increasing the vacancy concn. and by reducing local Li ordering. At higher temps. Li is gradually redistributed to the tetrahedral sites that can be occupied up to a site occupancy factor of 0.56. BV pathway anal. and closely harmonizing Li trajectories demonstrate that the two partially occupied Li sites of similar site energy form a 3D network suitable for fast ion conduction. The simulated diffusion coeff. and its activation energy closely match the exptl. conductivities. The degree of correlation of the vacancy-type Li+ ion migration is analyzed in terms of the van Hove correlation function.
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50. 50
  Jalem, R.; Rushton, M. J. D.; Manalastas, W., Jr.; Nakayama, M.; Kasuga, T.; Kilner, J. A.; Grimes, R. W. Effects of Gallium Doping in Garnet-Type Li₇La₃Zr₂O₁₂ Solid Electrolytes. Chem. Mater. 2015, 27, 2821– 2831, DOI: 10.1021/cm5045122
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  50
  Effects of Gallium Doping in Garnet-Type Li7La3Zr2O12 Solid Electrolytes
  Jalem, Randy; Rushton, M. J. D.; Manalastas, William; Nakayama, Masanobu; Kasuga, Toshihiro; Kilner, John A.; Grimes, Robin W.
  Chemistry of Materials (2015), 27 (8), 2821-2831CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
  Garnet-type Li7La3Zr2O12 (LLZrO) is a candidate solid electrolyte material that is now being intensively optimized for application in com. competitive solid state Li+ ion batteries. In this study we investigate, by force-field-based simulations, the effects of Ga3+ doping in LLZrO. We confirm the stabilizing effect of Ga3+ on the cubic phase. We also det. that Ga3+ addn. does not lead to any appreciable structural distortion. Li site connectivity is not significantly deteriorated by the Ga3+ addn. (>90% connectivity retained up to x = 0.30 in Li7-3xGaxLa3Zr2O12). Interestingly, two compositional regions are predicted for bulk Li+ ion cond. in the cubic phase: (i) a decreasing trend for 0 ≤ x ≤ 0.10 and (ii) a relatively flat trend for 0.10 < x ≤ 0.30. This cond. behavior is explained by combining analyses using percolation theory, van Hove space time correlation, the radial distribution function, and trajectory d.
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51. 51
  Deschanvres, A.; Raveau, B.; Sekkal, Z. Mise en evidence et etude cristallographique d’une nouvelle solution solide de type spinelle Li_1+xTi_2–xO₄ 0 ≤ x ≤ 0, 33₃. Mater. Res. Bull. 1971, 6, 699– 704, DOI: 10.1016/0025-5408(71)90103-6
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  Demonstration and crystallographic study of new spinel-type solid solution Li1+xTi1-3xTi1+2xO4 with O .leq. .tim. .leq. 0.33
  Deschanvres, A.; Raveau, B.; Sekkal, Z.
  Materials Research Bulletin (1971), 6 (8), 699-704CODEN: MRBUAC; ISSN:0025-5408.
  A new solid-soln. spinel type Li1+xTi3+1-3x-Ti4+1+2xO4 with O ≤ x ≤ 0.33 has been isolated. The positions of the different atoms in the cubic cell were detd.
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52. 52
  Ziebarth, B.; Klinsmann, M.; Eckl, T.; Elsasser, C. Lithium diffusion in the spinel phase Li₄Ti₅O₁₂ and in the rocksalt phase Li₇Ti₅O₁₂ of lithium titanate from first principles. Phys. Rev. B 2014, 89, 174301, DOI: 10.1103/PhysRevB.89.174301
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  Lithium diffusion in the spinel phase Li4Ti5O12 and in the rocksalt phase Li7Ti5O12 of lithium titanate from first principles
  Ziebarth, Benedikt; Klinsmann, Markus; Eckl, Thomas; Elsaesser, Christian
  Physical Review B: Condensed Matter and Materials Physics (2014), 89 (17), 174301/1-174301/7, 7 pp.CODEN: PRBMDO; ISSN:1098-0121. (American Physical Society)
  Lithium titanate (LTO) is a promising candidate as an anode material in future generations of lithium ion batteries due to its high intrinsic safety and stability. In this work, we investigate the diffusion barriers for lithium ions in two different crystal structures of LTO using the d. functional theory. Our calcns. show that the activation barriers vary between 0.30-0.48 eV for the spinel phase Li4Ti5O12 and between 0.20-0.51 eV in the lithiated rocksalt phase Li7Ti5O12. The origins of the rather broad ranges of activation energies are related to different chem. environments of the diffusion channels due to mixed occupancies of some sites in LTO. Our results reveal that the detn. of lithium diffusion consts. in LTO can not be carried out by using a single activation barrier. Instead, the local environment of the diffusion paths must be considered to correctly capture the variety of activation barriers. Moreover, we find the sites which have mixed occupation in LTO to trap lithium vacancies in the spinel phase. This effect is not obsd. in the rocksalt phase. This behavior explains the low lithium diffusivity found in expts. for lithium concns. in the vicinity of the spinel phase.
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  A cross-platform program, VESTA, has been developed to visualize both structural and volumetric data in multiple windows with tabs. VESTA represents crystal structures by ball-and-stick, space-filling, polyhedral, wire frame, stick, dot-surface and thermal-ellipsoid models. A variety of crystal-chem. information is extractable from fractional coordinates, occupancies and oxidn. states of sites. Volumetric data such as electron and nuclear densities, Patterson functions, and wavefunctions are displayed as isosurfaces, bird's-eye views and two-dimensional maps. Isosurfaces can be colored according to other phys. quantities. Translucent isosurfaces and/or slices can be overlapped with a structural model. Collaboration with external programs enables the user to locate bonds and bond angles in the 'graphics area', simulate powder diffraction patterns, and calc. site potentials and Madelung energies. Electron densities detd. exptl. are convertible into their Laplacians and electronic energy densities.
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  Giannozzi, P.; Baroni, S.; Bonini, N.; Calandra, M.; Car, R.; Cavazzoni, C.; Ceresoli, D.; Chiarotti, G. L; Cococcioni, M.; Dabo, I.; Dal Corso, A.; de Gironcoli, S.; Fabris, S.; Fratesi, G.; Gebauer, R.; Gerstmann, U.; Gougoussis, C.; Kokalj, A.; Lazzeri, M.; Martin-Samos, L.; Marzari, N.; Mauri, F.; Mazzarello, R.; Paolini, S.; Pasquarello, A.; Paulatto, L.; Sbraccia, C.; Scandolo, S.; Sclauzero, G.; Seitsonen, A. P; Smogunov, A.; Umari, P.; Wentzcovitch, R. M QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials. J. Phys.: Condens. Matter 2009, 21, 395502, DOI: 10.1088/0953-8984/21/39/395502
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  Generalized gradient approxns. (GGA's) for the exchange-correlation energy improve upon the local spin d. (LSD) description of atoms, mols., and solids. We present a simple derivation of a simple GGA, in which all parameters (other than those in LSD) are fundamental consts. Only general features of the detailed construction underlying the Perdew-Wang 1991 (PW91) GGA are invoked. Improvements over PW91 include an accurate description of the linear response of the uniform electron gas, correct behavior under uniform scaling, and a smoother potential.
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  First-principles calcns. within the local d. approxn. (LDA) or generalized gradient approxn. (GGA), though very successful, are known to underestimate redox potentials, such as those at which lithium intercalates in transition metal compds. We argue that this inaccuracy is related to the lack of cancellation of electron self-interaction errors in LDA/GGA and can be improved by using the DFT + U method with a self-consistent evaluation of the U parameter. We show that, using this approach, the exptl. lithium intercalation voltages of a no. of transition metal compds., including the olivine LixMPO4 (M = Mn, Fe Co, Ni), layered LixMO2 (x = Co, Ni) and spinel-like LixM2O4 (M = Mn, Co), can be reproduced accurately.
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  A change in the electronic spin state of the surfaces relevant to Li (de)intercalation of nanosized stoichiometric LiCo(III)O2 from low-spin to intermediate and high spin was obsd. for the 1st time. These surfaces are relevant for Li (de)intercalation. From DFT calcns. with Hubbard U correction, the surface energies of the layered Li Co oxide can be lowered as a consequence of the spin change. The crystal field splitting of Co d orbitals is modified at the surface due to missing Co-O bonds. The electronic spin transition also has an impact on Co(III)-Co(IV) redox potential, as revealed by the change in the Li (de)intercalation voltage profile in a Li half cell.
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  Unravelling Li-Ion Transport from Picoseconds to Seconds: Bulk versus Interfaces in an Argyrodite Li6PS5Cl-Li2S All-Solid-State Li-Ion Battery
  Yu, Chuang; Ganapathy, Swapna; de Klerk, Niek J. J.; Roslon, Irek; van Eck, Ernst R. H.; Kentgens, Arno P. M.; Wagemaker, Marnix
  Journal of the American Chemical Society (2016), 138 (35), 11192-11201CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
  One of the main challenges of all-solid-state Li-ion batteries is the restricted power d. due to the poor Li-ion transport between the electrodes via the electrolyte. However, to establish what diffusional process is the bottleneck for Li-ion transport requires the ability to distinguish the various processes. The present work investigates the Li-ion diffusion in argyrodite Li6PS5Cl, a promising electrolyte based on its high Li-ion cond., using a combination of 7Li NMR expts. and DFT based mol. dynamics simulations. This allows us to distinguish the local Li-ion mobility from the long-range Li-ion motional process, quantifying both and giving a coherent and consistent picture of the bulk diffusion in Li6PS5Cl. NMR exchange expts. are used to unambiguously characterize Li-ion transport over the solid electrolyte-electrode interface for the electrolyte-electrode combination Li6PS5Cl-Li2S, giving unprecedented and direct quant. insight into the impact of the interface on Li-ion charge transport in all-solid-state batteries. The limited Li-ion transport over the Li6PS5Cl-Li2S interface, orders of magnitude smaller compared with that in the bulk Li6PS5Cl, appears to be the bottleneck for the performance of the Li6PS5Cl-Li2S battery, quantifying one of the major challenges toward improved performance of all-solid-state batteries.
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  Groh, M. F.; Sullivan, M. J.; Gaultois, M. W.; Pecher, O.; Griffith, K. J.; Grey, C. P. Interface Instability in LiFePO₄-Li_3+xP_1-xSi_xO₄ All-Solid-State Batteries. Chem. Mater. 2018, 30, 5886– 5895, DOI: 10.1021/acs.chemmater.8b01746
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  Interface Instability in LiFePO4-Li3+xP1-xSixO4 All-Solid-State Batteries
  Groh, Matthias F.; Sullivan, Matthew J.; Gaultois, Michael W.; Pecher, Oliver; Griffith, Kent J.; Grey, Clare P.
  Chemistry of Materials (2018), 30 (17), 5886-5895CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
  All-solid-state batteries based on noncombustible solid electrolytes are promising candidates for safe and high energy storage systems, but it remains a challenge to prep. systems with stable interfaces between the various solid components that survive both the synthesis conditions and electrochem. cycling. The cathode mixts. based on carbon-coated LiFePO4 active material and Li3+xP1-xSixO4 solid electrolyte are investigated for potential use in all-solid-state batteries. Half-cells were constructed by combining both compds. into pellets by spark plasma sintering (SPS). The fast and quant. formation is reported of two solid solns. (LiFePO4-Fe2SiO4 and Li3PO4-Li2FeSiO4) for different compns. and ratios of the pristine compds., as tracked by powder X-ray diffraction and solid-state NMR; X-ray absorption near-edge spectroscopy confirms the formation of iron silicates similar to Fe2SiO4. SEM and energy dispersive X-ray spectroscopy reveal diffusion of iron cations up to 40 μm into the solid electrolyte even in the short processing times accessible by SPS. Electrochem. cycling of the SPS-treated cathode mixts. demonstrates a substantial decrease in capacity following the formation of the solid solns. during sintering. Consequently, all-solid-state batteries based on LiFePO4 and Li3+xP1-xSixO4 would necessitate iron ion blocking layers. More generally, this study highlights the importance of systematic studies on the fundamental reactions at the active material-solid electrolyte interfaces to enable the introduction of protective layers for com. successful all-solid-state batteries.
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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsaem.0c02033.
- Calculated bulk structures and vacancy formation energies of LCO, LPS, LPO, and LLZO; structure models, projected density of states, representative sampled structures, site-dependent vacancy formation energies, cation mixing energies, obtained in the calculations of the LCO(104)/LPS(010), LCO(110)/LPS(010), LCO(104)/LPO(001), LCO(104)/LPO(010), LCO(110)/LPO(010), LCO(104)/LLZO(001), LTO(111)/LPS(010), and LCO(104)/LTO(111) interfaces (PDF)
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Comparative Study on Sulfide and Oxide Electrolyte Interfaces with Cathodes in All-Solid-State Battery via First-Principles Calculations

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Abstract

1. Introduction

2. Calculation

2.1. Interface Construction

Figure 1

2.2. Computational Details

3. Results and Discussion

3.1. LCO/LPS Interface

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3.2. LCO/LPO Interface

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3.3. LCO/LLZO Interface

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3.4. Interface of Oxide Buffer Layer LTO

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4. Summary

Supporting Information

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Author Information

Acknowledgments

References

Cited By

Abstract

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References

Supporting Information

Supporting Information

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STEP 1:

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