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Drastic Reduction of the Solid Electrolyte–Electrode Interface Resistance via Annealing in Battery Form
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Energy, Environmental, and Catalysis Applications

Drastic Reduction of the Solid Electrolyte–Electrode Interface Resistance via Annealing in Battery Form
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ACS Applied Materials & Interfaces

Cite this: ACS Appl. Mater. Interfaces 2022, 14, 2, 2703–2710
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https://doi.org/10.1021/acsami.1c17945
Published January 6, 2022

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Abstract

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The origin of electrical resistance at the interface between the positive electrode and solid electrolyte of an all-solid-state Li battery has not been fully determined. It is well known that the interface resistance increases when the electrode surface is exposed to air. However, an effective method of reducing this resistance has not been developed. This report demonstrates that drastic reduction of the resistance is achievable by annealing the entire battery cell. Exposing the LiCoO2 positive electrode surface to H2O vapor increases the resistance by more than 10 times (to greater than 136 Ω cm2). The magnitude can be reduced to the initial value (10.3 Ω cm2) by annealing the sample in a battery form. First-principles calculations reveal that the protons incorporated into the LiCoO2 structure are spontaneously deintercalated during annealing to restore the low-resistance interface. These results provide fundamental insights into the fabrication of high-performance all-solid-state Li batteries.

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Introduction

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All-solid-state Li batteries have become promising next-generation batteries owing to their high energy density and charge–discharge cyclability. (1) However, the large resistance at the interface between the solid electrolyte and positive electrode (electrolyte–electrode interface resistance) considerably deteriorates their performance. (2,3) In the proposed mechanisms of the increased interface resistance, one of the most plausible origins of the increased interface resistance is the chemical side reaction at the interface. (4−10) The atmospheric gas adsorption on the electrode surface significantly deteriorates the interface resistance, (11,12) and the battery capacity and cyclic performance are degraded. (13,14) Although there have been many attempts to decrease the interface resistance, such as by introducing oxide buffer layers, (15,16) no method can restore the resistance to ∼10 Ω cm2, which is close to the lowest solid-electrolyte–electrode interface resistance reported. (17) Establishing a strategy for recovering the low interface resistance is critically important for the development of all-solid-state Li batteries.
Thin-film Li batteries provide suitable platforms for studying interfacial phenomena. They enable the quantitative investigation of interface resistances by defining the areas and crystal structures of electrolyte–electrode interfaces. (18,19) In vacuo fabrication techniques enable the fabrication of electrolyte–electrode interfaces with very low resistance values. (17) Such low-resistance interfaces will enable the investigation of factors, such as gas exposure, which could affect the interface phenomena by manipulating them individually. Such bottom-up studies will lead to an advanced foundation of solid-state physics that is combined with electrochemistry.
This paper reports the recovery of a low interface resistance and elucidates its reduction mechanism. First, we demonstrate that, among the different gas species present in air, only H2O vapor strongly degrades the Li3PO4–LiCoO2 interface and drastically increases its resistance. Next, we show that the low interface resistance can be recovered by annealing the sample in a battery form (after depositing the negative electrode). Finally, we discuss the low resistance recovery atomistic mechanism determined from the results of structural analysis and first-principles calculations. We emphasize that the protons in the LiCoO2 structure play an important role in the recovery process.

Results

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Fabrication of Gas-Exposed Batteries and Their Performance Characteristics

We fabricated the thin-film batteries consisting of an Li negative electrode with a thickness (t) of 1 μm, an amorphous Li3PO4 solid electrolyte (t = 1 μm), an LiCoO2 positive electrode (t = 40 nm), an Au current collector (t = 100 nm), and an Al2O3 (0001) substrate (Figure S1). The interfaces between the Li3PO4 and LiCoO2 layers were intentionally exposed to air, N2, O2, CO2, H2, and H2O gas (hereafter referred to as the air-, N2-, O2-, CO2-, H2-, and H2O-exposed batteries, respectively) for 30 min. We also prepared a nonexposed battery (in vacuo) as a reference (see the Methods section for the details of the fabrication procedure).
Figure 1a,b compares the CV curves of the in vacuo and air-exposed thin-film batteries. The in vacuo battery exhibits sharp current peaks at 3.94 and 3.88 V vs Li+/Li, corresponding to the extraction and insertion of Li ions, respectively. In contrast, the air-exposed battery generates relatively weak peaks, indicating that exposing the electrode surface to air strongly degrades the battery performance.

Figure 1

Figure 1. Electrochemical characteristics of the (a, c, and e) in vacuo and (b, d, and f) air-exposed batteries. cyclic voltammetry (CV) curves of the (a) in vacuo and (b) air-exposed batteries. The voltage was swept at a rate of 1 mV·s–1 from 3.0 to 4.3 V vs Li+/Li. The displayed curves correspond to the 20th charge–discharge cycle. Impedance spectra of the (c) in vacuo and (d) air-exposed batteries recorded at voltages of 3.8 and 4.2 V vs Li+/Li. The numbers n in the plots indicate frequencies (10n Hz). Low-frequency regions of the impedance spectra recorded for the (e) in vacuo and (f) air-exposed batteries. The fitting data obtained for the equivalent circuit at 4.2 V vs Li+/Li data (Table S1) are shown as colored semicircles. The light-green semicircle denotes the resistance of Li ion conduction in the Li3PO4 solid electrolyte. The gray semicircle represents the Li3PO4–LiCoO2 interface resistance (10.9 Ω·cm2 for the in vacuo battery and 200 Ω·cm2 for the air-exposed battery).

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The AC impedance spectra obtained for both batteries contain clear semicircles in the frequency range of 102–105 Hz (Figure 1c,d). Because these semicircles are observed both in the charged and discharged states (4.2 and 3.8 V vs Li+/Li), they likely originate from the impedance of the Li3PO4 solid electrolyte. The ionic conductivity of Li3PO4 estimated from the impedance spectra is 4.9 × 10–7 S cm–1, which is in good agreement with the previously reported values. (20) In addition to the semicircle in the high-frequency region, a semicircle associated with the electrolyte–electrode interface is observed in the 101–102 Hz frequency range. The fit of the semicircle in Figure 1e,f results in an interface resistance of 10.9 Ω·cm2 for the in vacuo battery and 200 Ω cm2 for the air-exposed battery (see the detailed analysis in Figure S2). The increase in the interface resistance observed after air exposure is consistent with the results obtained by Iriyama et al. (11)
Next, we discuss the effects of exposing the electrode surfaces to pure gases (N2, O2, CO2, H2, and H2O) on the interface resistance. Initially, we expected that these gas molecules would react with Li ions in the LiCoO2 lattice to form a resistive layer on the electrode surface. However, a typical interface resistance of the N2-exposed batteries is 9.6 Ω·cm2, which is very close to that of the in vacuo battery. In addition, comparable resistance values (∼10 Ω·cm2) were obtained for the O2-, CO2-, and H2-exposed batteries, indicating that N2, O2, CO2, and H2 gases did not degrade the interfaces (Table 1; Figure S3d–l).
Table 1. Interface Resistances of the Gas-Exposed Batteries
 exposed gas species
 in vacuoairN2CO2O2H2H2O
interface resistance at 4.2 V vs Li+/Li (Ω·cm2)10.92009.68.316.513.4>136
In contrast, H2O vapor exposure drastically degrades the battery performance. The peak current in the corresponding CV curve is ∼20 nA (10 mA/cm2, Figure 2a) at a voltage of 3.9 V vs Li+/Li, which is much smaller than the magnitude obtained for the in vacuo battery (approximately 200 nA (100 mA/cm2); see Figure 1a). It was difficult to determine the interface resistance of the H2O-exposed battery accurately because of the strong electrode degradation. Therefore, we speculate that the interface resistance is underestimated. We estimated its value to be greater than 136 Ω·cm2, which was at least 12 times larger than that of the in vacuo interface (Figure S4). H2O is the only species that increases the interface resistance; therefore, it is very important to recover the deteriorated interface after H2O exposure. (21)

Figure 2

Figure 2. (a) CV curves of the H2O-vapor-exposed battery recorded before (blue) and after (red) annealing in an Ar atmosphere at a temperature of 150 °C and pressure of 1 atm for 60 min. The measurements were conducted after the samples had been cooled down to ambient temperature. The voltage was swept in the range from 3.0 to 4.3 V vs Li/Li+ at a rate of 1 mV·s–1. (b) Impedance spectra recorded at voltages of 3.8 and 4.2 V vs Li+/Li for the H2O-vapor-exposed battery after annealing. The numbers denote the frequencies. (c) Dependence of the interface resistance on the annealing time obtained at a voltage of 4.2 V vs Li+/Li and an annealing temperature of 150 °C. The interface resistances were measured after cooling the sample to room temperature (27 °C). (d) Annealing temperature dependences of the interface resistance obtained at a voltage 4.2 V vs Li+/Li and annealing times of 60 and 120 min.

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Reduction of the Interface Resistance by Battery Annealing

To our surprise, the annealing of the battery drastically reduced the interface resistance and restored the original battery performance. We annealed a sample after depositing Li3PO4 and an Li negative electrode. Figure 2a shows the CV curve of the H2O-vapor-exposed battery recorded after annealing at 150 °C in an Ar atmosphere for 60 min (hereafter called the battery-annealed sample). The peak current at the 20th cycle (∼3.9 V vs Li/Li+) is more than 90% of that of the in vacuo battery with the same electrode thickness. Moreover, the corresponding interface resistance is 10.3 Ω·cm2 (Figure 3b), which is comparable to the value obtained for the in vacuo battery (10.9 Ω·cm2). Furthermore, the cyclic battery performance was comparable to that of the in vacuo battery (Figure S5). The air-exposed batteries also showed recovery from 200 to 21.8 Ω·cm2 (Figure S6).

Figure 3

Figure 3. (a) X-ray crystal truncation rod (CTR) scattering profiles of the pristine (in vacuo, black), H2O-vapor-exposed (blue), and annealed (red) battery samples. The spectra were recorded after depositing Li3PO4 layers on the LiCoO2 surfaces. An Li thin film was deposited only on the Li3PO4 layer of the annealed battery sample. The thicknesses of the LiCoO2, Li3PO4, and Li thin films were 5 nm, 500 nm, and 1 μm, respectively. (b) Electron density profiles of the in vacuo, H2O-vapor-exposed, and annealed battery samples derived from the results of structural analyses of the corresponding CTR profiles. Owing to the existence of the antiphase domain, the electron density of the Li layer appears to be larger than the actual electron density of Li.

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The degree of battery performance recovery depends on the annealing duration and temperature. As the time of annealing at 150 °C increases from 15 to 60 min, the interface resistance decreases, whereas it remains constant beyond 60 min (Figure 2c). In addition, we annealed the H2O-vapor-exposed samples for 60 and 120 min at various temperatures (Figure 2d). The interface resistance is lower at higher annealing temperatures and is saturated beyond an annealing duration of 60 min at each temperature. These results suggest that multiple thermodynamic factors play important roles in the recovery process.

Dependence of Performance Recovery on Stacking Conditions

To reveal the recovery mechanism, we annealed the sample with two different structures. First, an H2O-vapor-exposed LiCoO2 thin film was annealed without depositing Li3PO4 or Li metal. The LiCoO2 surface was annealed immediately after exposure (Figure S7a) at 200 °C for 60 min in a vacuum (<1 × 10–5 Pa) to desorb H2O molecules. After cooling to room temperature, Li3PO4 and Li electrode layers were deposited to form a battery. Although heating was performed at a temperature significantly exceeding the evaporation temperature of water in a vacuum, we observed no reduction in the interface resistance, and the solid-electrolyte–electrode interface remained degraded (Figure S7b,c).
The second method involved annealing the sample after Li3PO4 deposition, similarly to the procedure used in earlier studies (Figure S7b). (8,9) The LiCoO2 surface was exposed to H2O followed by the Li3PO4 deposition. Subsequently, the sample was annealed at 150 °C in an Ar atmosphere (1 atm) for 60 min. After the sample had been cooled to room temperature, an Li negative electrode was deposited to form a battery. The results showed that the CV peak current considerably increased, whereas the interface resistance decreased to 125 Ω·cm2 (Figure S7e,f). The latter was still an order of magnitude larger than the interface resistances of the in vacuo batteries. These investigations indicate that the battery structure is crucial for recovery.

Structural Analysis of the H2O-Vapor-Exposed Battery Interface

Next, the atomic structures of the H2O-vapor-exposed LiCoO2 film after the battery annealing were investigated. The obtained X-ray CTR scattering data indicate that the CoO2 layers near the LiCoO2 surface are robust. Figure 3a shows the diffraction patterns in which the horizontal axis represents the Miller index L in the direction normal to the thin-film surface. For all three battery samples (in vacuo, H2O-vapor-exposed, and annealed), the LiCoO2 003n (n = integer) Bragg peaks are located at the same positions, and thickness fringes are observed. These results suggest that the crystallinity degree of interface LiCoO2 remains high even after H2O vapor exposure and annealing treatment and that no secondary phase layer is formed in the LiCoO2 layers. The electron density profiles derived from the CTR scattering data contain sharp peaks even on the surfaces (Li3PO4–LiCoO2 interfaces) of the three different battery types (Figure 3b). Hence, the CoO2 layers remained intact after reaction with the H2O species. These results indicate that H critically contributes to the degradation and annealing recovery.

Discussion

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This section suggests a plausible mechanism of the interface resistance recovery proposed by density functional theory (DFT) calculations. Previous studies of H2O-vapor-exposed LiCoO2 surfaces using X-ray photoemission and absorption spectroscopy techniques (22,23) suggest that the formation of Li vacancies and incorporation of protons from dissociated H2O into the LiCoO2 crystal produce H-incorporated LiCoO2 species. (24) Furthermore, the X-ray CTR scattering data confirm the intactness of the layered structures (Figure 3b). Thus, the battery recovery process should involve filling the Li vacancies with Li atoms and removing protons from the LiCoO2 lattice.
The first-principles calculations predict that protons are spontaneously removed from LiCoO2 because of the differences between the electrochemical potentials of the protons in the LiCoO2 and Li structures. In other words, an all-solid-state proton battery (25) is spontaneously formed after Li electrode deposition. Thus, the proton battery self-discharges during the annealing process. Considering the charge neutrality of LiCoO2, the following reaction should occur at the Li3PO4–LiCoO2 interface:
(1)
Deintercalated protons migrate through the Li3PO4 electrolyte to the Li negative electrode side. Indeed, proton conductivity has previously been reported for the H3PO4 structure, (26) which has the same anionic structure as Li3PO4. (27) Inversely, Li ions migrate from the Li negative electrode through the Li3PO4 electrolyte layer to fill the vacant sites in the Li1–xCoO2 structure.
To verify this hypothesis, we performed first-principles calculations for various types of intrinsic defects and a proton in the LiCoO2 lattice. The obtained defect formation energies confirmed that Li vacancies were dominant among Li, Co, and O vacancies in the bulk LiCoO2. This result is consistent with the data reported previously. (28) Therefore, it is reasonable to consider the formation of Li vacancies upon H2O vapor exposure. When these vacancies are present in the crystal structure, EF is located at the top of the valence band (EF ≈ 0.0 eV), which matches the results of previous theoretical (29) and experimental (30) studies. Hence, Li1–xCoO2 represents a heavily doped p-type semiconductor. (31)
Next, we discuss the incorporation of protons into the LiCoO2 lattice. First, we considered a proton located at the Li vacancy site; however, the energy of this structure was higher than that of the interstitial site (Figure S8). Using the same method, we calculated the energies of several configurations containing interstitial protons in the LiCoO2 lattice (Figure S9). Their optimized structures depicted in Figure 4a indicate that the interstitial proton is strongly bonded to the O atoms in LiCoO2. (32) The measured O–H bond length is approximately 0.99 Å (Figure 4a) with a proton donating a charge of ∼0.5e. This value is close to the O–H bond length in H2O gas molecules (0.958 Å). (33)

Figure 4

Figure 4. (a) Left: optimized crystal structure of the bulk LiCoO2 unit cell with an interstitial H atom. Right: schematic of H–O bonding at the most stable site. The adjacent Li atom is shifted from the O and H atoms. The structures were visualized using the VESTA software package. (33) (b) Formation energies of the neutral and charged H interstitials in the bulk LiCoO2 structures plotted as functions of the Fermi energy (EF) with respect to the valence-band maximum. The H partial pressure was set to pH2 ≈ 10–9 atm. The kinks correspond to the (+/0) charge transition levels. (c) Energy diagram constructed for the diffusion of an interstitial H from the most stable site to the closest neighboring stable site. The activation energy (Eact) of the proton diffusion process was estimated by considering the zero-point energies of the initial and transition states. (d) Diffusion coefficients estimated for an interstitial H atom in the LiCoO2 structure at different annealing temperatures.

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Figure 4b shows the formation energy of proton interstitials as a function of EF at different temperatures (T) and the low H partial pressure pH2 ≈10–4 Pa. The calculation results indicate that H0 species are unstable, whereas protons are formed when EF is near the top of the valence band. This result is consistent with the findings of a previous study on H defects in the p-type GaN, which stated that H solubility is significantly higher in p-type semiconductors. (31,34) Note that near the annealing temperature T ∼ 400 K, the formation energy of protons is shifted by approximately 0.9 eV from 0 K, indicating a decrease in stability with increasing temperature. These results are consistent with the removal of interstitial protons during annealing.
On the negative electrode side, there is a possibility of LiH formation due to the reaction of protons and Li. (35) The calculated Gibbs energies of the formation of LiH and proton interstitials in LiCoO2 are −0.765 and −0.153 eV, respectively. Therefore, protons are thermodynamically more stable in Li than in the LiCoO2 structure, leading to the spontaneous recovery of LiCoO2 after the deposition of the Li negative electrode. Furthermore, annealing the battery structure promotes proton migration and, therefore, the battery recovery process. In this work, we estimated the activation energy (Ea) of the proton migration in the LiCoO2 lattice, assuming that proton hopping involved only jumps from stable sites to the neighboring stable sites (Figure 4a). Figure 4c shows the energy barrier of the proton diffusion process. The Ea value estimated from the difference between the lowest energy and that of the saddle point is 1.41 eV at 0 K. Its magnitude is decreased to 1.278 eV when the zero-point energies of the initial state (0.333 eV) and transition state (0.201 eV) are considered (Figure 4d).
We can estimate the temperature at which the protons are sufficiently mobile from the condition that the calculated hopping rate (see the Methods section) is higher than 1 Hz. The calculated result is 495 K, which is comparable to the maximal experimental annealing temperature of 433 K. The diffusion coefficient of protons in the LiCoO2 structure increases with temperature (Figure 4d), and its value was estimated to be ∼10–17 cm2 s–1 at 433 K.
To validate the proposed recovery mechanism of hydrogen deintercalation, we measured the amount of protons using negative-ion time-of-flight secondary ion mass spectroscopy (ToF-SIMS). We tracked the ion signals of OH–, Li–, Al–, P–, and Co– in the battery cell. The amount of protons was evaluated based on the amount of OH–. First, we confirmed the hydrogen background level in the clean interface of Li3PO4 and LiCoO2 (Figure 5a). Before exposure to H2O, the ratio of the intensity of OH–, hydrogen species, to the Co– intensity of the LiCoO2 layer is 0.29 at a point at the center of the LiCoO2 layer. In contrast, the magnitude of the intensities of Co– and OH– is reversed after H2O exposure, and the ratio increases to 1.54 (Figure 5b). The exposed H2O-vapor-derived H diffuses into LiCoO2. Finally, after Li deposition and battery annealing, the intensity ratio is reduced to 0.56 (Figure 5c). This finding is consistent with the proton deintercalation results from LiCoO2 discussed in relation to the DFT calculations. Battery annealing was found to contribute to the normalization of the composition in the positive electrode.

Figure 5

Figure 5. (a–c) Negative ion time-of-flight secondary ion mass spectroscopy spectra for OH–, Al–, P–, and Co–. Figure S10 presents the data for Li– and H–. The green and blue regions represent Li3PO4 and LiCoO2, respectively. The signals of Al–, P–, and Co– were used to identify the interfaces. (a) Sample without H2O exposure, (b) H2O-vapor-exposed battery, and (c) battery annealed after H2O vapor exposure. An Li layer was deposited on the annealed sample only. (d) Schematic illustration of the battery performance deterioration with a large interface resistance caused by water adsorption and recovery of the low interface resistance via battery annealing.

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Conclusions

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In this study, the recovery of low electrolyte–electrode interface resistance was achieved by annealing the entire battery. Among the gas species present in air, only H2O degraded the interface between the amorphous Li3PO4 solid electrolyte and (001)-oriented LiCoO2 positive electrode, considerably increasing its resistance. The influence of protons on the properties of the solid-electrolyte–positive electrode interface was significant; however, during the fabrication of the battery structure, protons spontaneously migrated from LiCoO2 to the Li electrode through the Li3PO4 electrolyte (Figure 5d). The formation of a proton battery successfully recovered the initial low-resistance interface. The elucidation of the interfacial microscopic processes can help widen the application range of solid-state batteries.

Methods

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Fabrication of the Gas-Exposed Thin-Film Batteries

Thin-film deposition and sample transfer were performed inside an all-in-vacuum (in vacuo) system (13) except for the intentional gas exposures. An Au current collector (thickness: 100 nm) was deposited on an Al2O3 (0001) single crystal substrate by direct-current magnetron sputtering (power: 30 W, Ar gas partial pressure: 0.5 Pa) and annealed in a vacuum (<1 × 10–5 Pa) at a substrate temperature (Ts) of 600 °C. An LiCoO2 positive electrode (thickness: 40 nm) was deposited by radio frequency (RF) magnetron sputtering (power: 150 W, Ts = 600 °C, and Ar partial pressure: 0.5 Pa) using an Li1.2CoO2+δ target (Toshima Manufacturing Co. Ltd., Japan) followed by postdeposition annealing (Ts = 600 °C; O2 partial pressure: ∼9 Pa). The LiCoO2 surface was exposed to air or pure gas molecules (N2, CO2, O2, H2, and H2O) inside a high-vacuum gas-exposure chamber (<5 × 10–5 Pa). Table 2 lists the utilized exposure conditions. After the exposure, the chamber was re-evacuated to the vacuum and transferred back to the thin-film deposition chamber. An Li3PO4 solid electrolyte layer (thickness: 1 μm) was deposited by RF magnetron sputtering (power: 100 W; Ar partial pressure: 0.15 Pa). An Li metal negative electrode (thickness: 1 μm) was deposited by thermal evaporation. Both the Li3PO4 and Li layers were deposited on the unheated surfaces. Figure S1 shows the shapes and sizes of the prepared samples.
Table 2. Various Gas Species Exposed under Different Conditions
 conditions
gas speciespressure (Pa)exposure time (min)
N2∼1 × 10530
O2∼1 × 10530
CO2∼1 × 10530
H2∼1 × 10330
H2O∼2 × 10230
Air∼1 × 10530

Characterization of Thin Films and Battery Performance Evaluation

Electrochemical measurements were performed at room temperature (27 °C) inside an Ar-filled glove box (O2 < 0.5 ppm; H2O < 0.25 ppm) using a frequency response analyzer (Biologic SP-150). The detailed interface resistance determination process is described in Figure S2. The thicknesses of the obtained thin films were determined using a Stylus profiler (Veeco, Dek-Tak 150).

X-ray CTR Scattering Analysis

X-ray CTR scattering analysis (36) was performed to determine the stacking structure of the LiCoO2 layers. For the atomic-scale analysis, we used LiCoO2 epitaxial thin films on an Al2O3(0001) single crystalline substrate prepared by pulsed laser deposition with a KrF excimer laser (see the Supplementary Information for the details of the deposition process). The battery-annealed sample was placed in a vacuum sample cell (<1 × 10–4 Pa) during the measurements to avoid the deterioration of the Li layer. Other samples without Li layers were placed in a sample cell with He gas flow during the measurements. The CTR measurements were performed at the BL13XU beamline of the SPring-8 synchrotron radiation facility and BL-3A beamline of the Photon Factory, KEK. The incident X-ray energy was 11 keV, and the scattered X-rays were detected using a two-dimensional detector (PILATUS-100 K). The antiphase domain was considered in the analysis of the electron density profile. (37)

DFT Calculation

To gain insight into the H defects of the LiCoO2 structure, we performed first-principles calculations using the projector augmented-wave method (38) with a plane-wave cutoff energy of 520 eV and the optPBE-vdW functional (39−41) implemented in the VASP software package. (42) We used a gamma-centered 5 × 5 × 5 k-points set for Brillouin zone integration. The electron correlations in the 3d orbitals of LiCoO2 Co atoms were considered through onsite Hubbard correction (DFT + U, U = 3.32 eV). (43) The calculations produced a bandgap of approximately 2.1 eV for pristine LiCoO2 and an open-circuit voltage (VOC) of approximately 4.07 V. The stability of a point defect X in a charge state q was determined from the formation energy via the following formula: (44)
(2)
where ET(Xq) and ET(LCO) are the DFT total energies of the defective system and bulk LiCoO2 supercell, respectively; ni is the number of atomic species i with chemical potential μi that are removed from (ni < 0) or added to (ni > 0) the supercell; EVBM is the energy corresponding to the valence-band maximum (VBM); EF is the Fermi energy; and Δcorrq accounts for the spurious interactions between the charged defects and periodic supercell images. (45)EF can be derived by equating the sums of the concentrations of all negative and positive defects, which requires estimation of the formation energies of all intrinsic defects in the bulk LiCoO2 structure.
We obtained the total energies by performing DFT simulations on a 108-atom 3 × 3 × 1 LiCoO2 supercell. To determine the Li chemical potential at the positive electrode, we set the negative electrode as a reference and assumed μLi = – eVOC = – 4.07 eV for all Ef(Xq). The chemical potential of H defects was calculated as , (46) where the first term corresponds to half of the total DFT energy of an H2 molecule in the gas phase at 0 K, and the last two terms account for the effects of temperature and the hydrogen partial pressure. The migration barrier was estimated by computing the total energy curve of a fixed H atom at different positions along the path connecting the initial and final states while allowing the surrounding atoms to relax. The diffusion coefficient was calculated as follows: (47), where . Ea is the activation energy, n is the number of sites, d is the dimension, and r is the jump length. The prefactor (attempt frequency) THz ∼1013 Hz was derived from the DFT simulation results using Vineyard’s method. (44) Here, viIS and viTS are the DFT vibrational frequencies of the initial and transition states, respectively. We calculated the annealing temperature by assuming a jump rate of 1 Hz (48) and using our computed prefactor.

Negative ion ToF-SIMS analysis

To confirm the hydrogen distribution across the thin-film battery, we analyzed the H2O-vapor-exposed Li3PO4–LiCoO2 interface by performing ToF-SIMS. A primary beam with 60 keV Bi3+ and a measured current of 0.06 Pa were used for the analysis. The sputtering was performed with 2 keV Cs+ ions on a 300 μm square area, and analysis was performed in a 100 μm square.

Supporting Information

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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsami.1c17945.

  • Fabrication of gas-exposed thin-film batteries, X-ray crystal truncation rod (CTR) scattering analysis, estimation of the interface resistance using an equivalent circuit, electrochemical properties of the pure gas-exposed batteries, impedance spectra of the H2O-vapor-exposed battery, parameters of the equivalent circuits used for the gas-exposed batteries, capacity retention, annealing recovery of the air-exposed battery, annealing processes and performance of the H2O-vapor-exposed battery, parameters of the equivalent circuits used for the gas-exposed batteries after the annealing process, optimized geometry of a proton occupying a Li vacancy site in the LiCoO2 structure, comparison of different LCO proton interstitial sites, and the time-of-flight secondary ion mass spectroscopy spectrum for H– and Li– species (PDF)

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Author Information

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  • Corresponding Authors
  • Authors
    • Elvis F. Arguelles - Department of Materials Engineering, The University of Tokyo, Tokyo 113-8656, Japan
    • Tetsuroh Shirasawa - National Metrology Institute of Japan, National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba, Ibaraki 305-8565, Japan;  Orcidhttps://orcid.org/0000-0001-5519-6977
    • Shusuke Kasamatsu - Faculty of Science, Yamagata University, Yamagata 990-8560, Japan;  Orcidhttps://orcid.org/0000-0002-4368-7995
    • Koji Shimizu - Department of Materials Engineering, The University of Tokyo, Tokyo 113-8656, Japan
    • Kazunori Nishio - School of Materials and Chemical Technology, Tokyo Institute of Technology, Meguro, Tokyo 152-8552, Japan;  Orcidhttps://orcid.org/0000-0002-8201-358X
    • Yuki Watanabe - School of Materials and Chemical Technology, Tokyo Institute of Technology, Meguro, Tokyo 152-8552, Japan;  Orcidhttps://orcid.org/0000-0003-2589-1105
    • Yusuke Kubota - Tokyo Electron Technology Solutions Limited, 650 Mitsuzawa, Hosaka−cho, Nirasaki, Yamanashi 407-0192, Japan
    • Ryota Shimizu - School of Materials and Chemical Technology, Tokyo Institute of Technology, Meguro, Tokyo 152-8552, Japan;  PRESTO, Japan Science and Technology Agency, Kawaguchi, Saitama 332-0012, Japan;  Orcidhttps://orcid.org/0000-0001-9600-7255
    • Satoshi Watanabe - Department of Materials Engineering, The University of Tokyo, Tokyo 113-8656, Japan;  Orcidhttps://orcid.org/0000-0002-8069-6938
  • Author Contributions

    S.Ko., Y.K., R.S., and T.H. designed the experiments. S.Ko. contributed to the fabrication and characterization of the thin films and thin-film batteries. E.F.A. contributed to the first-principles calculations of the hydrogen defect in the thin-film materials. T.S. contributed to the measurement and structural analysis of synchrotron X-ray CTR scattering. S.Ka., K.S., and S.W. supported the first-principles calculations and discussed the calculation settings. Y.W. and K.N. supported the thin-film fabrications. S.Ko. and T.H. wrote the manuscript with help from all of the co-authors.

  • Notes
    The authors declare no competing financial interest.

Acknowledgments

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We thank Kazuhiko Kikuchi and Haruo Nagasawa (Pascal Co.) for experimental support. We thank Dr. Daiki Katsube (Nagaoka University of Technology) for technical advice on H2O vapor purification. We thank Akira Genseki at the Center for Advanced Materials Analysis, Tokyo Institute of Technology, for assistance with the ToF-SIMS measurements. We also thank Dr. Toshiya Saito (Toyota Corporation) and Prof. Clare P. Grey (University of Cambridge) for fruitful discussions. E.F.A. acknowledges funding from JSPS KAKENHI (grant no. 19K15397), Japan. R.S. acknowledges funding from JSPS KAKENHI (grant no. 17H05216) and JST–PRESTO (grant no. JPMJPR17N6), Japan. T.H. acknowledges funding from JSPS KAKENHI (grant nos. JP18H03876 and JP18H05514) and the JST–CREST (grant no. JPMJCR1523) program. The X-ray CTR experiments were conducted at the SPring–8 synchrotron radiation facility (proposal Nos. 2018A1256 and 2018B1286) and Photon Factory, KEK (PF–PAC No. 2019G056). We would like to thank Editage (www.editage.jp) for English language editing.

References

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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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    17
    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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  18. 18
    Kuwata, N.; Iwagami, N.; Tanji, Y.; Matsuda, Y.; Kawamura, J. Characterization of Thin-film Lithium Batteries with Stable Thin-film Li3PO4 Solid Electrolytes Fabricated by ArF Excimer Laser Deposition. J. Electrochem. Soc. 2010, 157, A521– A527,  DOI: 10.1149/1.3306339
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    18
    Characterization of Thin-Film Lithium Batteries with Stable Thin-Film Li3PO4 Solid Electrolytes Fabricated by ArF Excimer Laser Deposition
    Kuwata, Naoaki; Iwagami, Naoya; Tanji, Yoshinari; Matsuda, Yasutaka; Kawamura, Junichi
    Journal of the Electrochemical Society (2010), 157 (4), A521-A527CODEN: JESOAN; ISSN:0013-4651. (Electrochemical Society)
    High quality Li3PO4 thin films have been prepd. by pulsed laser deposition (PLD) as a solid electrolyte for thin-film batteries. The structure, compn., ionic cond., and electrochem. stability of the Li3PO4 thin films have been characterized. The Li3PO4 film exhibits a single lithium-ion conductor with an ionic cond. of 4.0 × 10-7 S/cm at 25° and an activation energy of 0.58 eV. The Li3PO4 film is electrochem. stable in the potential range 0-4.7 V vs. Li/Li+. All-solid-state thin-film batteries, Li/Li3PO4/LiCoO2, have been fabricated by using PLD-grown Li3PO4 thin film. The thin-film battery shows excellent intercalation property and stability for long-term cycling in the potential range 3.0-4.4 V.
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  19. 19
    Garcia, B.; Farcy, J.; Pereira-Ramos, J. P.; Baffier, N. Electrochemical Properties of Low Temperature Crystallized LiCoO2. J. Electrochem. Soc. 1997, 114, 1179– 1184
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    Bates, J. B.; Dudney, N. J.; Gruzalski, G. R.; Zuhr, R. A.; Choudhury, A.; Luck, C. 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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  21. 21
    Zou, L.; He, Y.; Liu, Z.; Jia, H.; Zhu, J.; Zheng, J.; Wang, G.; Li, X.; Xiao, J.; Liu, J.; Zhang, J. G.; Chen, G.; Wang, C. Unlocking the Passivation Nature of the Cathode–Air Interfacial Reactions in Lithium Ion Batteries. Nat. Commun. 2020, 11, 3204,  DOI: 10.1038/s41467-020-17050-6
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    Unlocking the passivation nature of the cathode-air interfacial reactions in lithium ion batteries
    Zou, Lianfeng; He, Yang; Liu, Zhenyu; Jia, Haiping; Zhu, Jian; Zheng, Jianming; Wang, Guofeng; Li, Xiaolin; Xiao, Jie; Liu, Jun; Zhang, Ji-Guang; Chen, Guoying; Wang, Chongmin
    Nature Communications (2020), 11 (1), 3204CODEN: NCAOBW; ISSN:2041-1723. (Nature Research)
    It is classically well perceived that cathode-air interfacial reactions, often instantaneous and thermodn. non-equil., will lead to the formation of interfacial layers, which subsequently, often vitally, control the behavior and performance of batteries. However, understanding of the nature of cathode-air interfacial reactions remain elusive. Here, using at.-resoln., time-resolved in-situ environmental transmission electron microscopy and atomistic simulation, we reveal that the cathode-water interfacial reactions can lead to the surface passivation, where the resultant conformal LiOH layers present a crit. thickness beyond which the otherwise sustained interfacial reactions are arrested. We rationalize that the passivation behavior is dictated by the Li+-water interaction driven Li-ion de-intercalation, rather than a direct cathode-gas chem. reaction. Further, we show that a thin disordered rock salt layer formed on the cathode surface can effectively mitigate the surface degrdn. by suppressing chem. delithiation. The established passivation paradigm opens new venues for the development of novel high-energy and high-stability cathodes.
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    Motzko, M.; Carrillo Solano, M. A.; Jaegermann, W.; Hausbrand, R. Photoemission Study on the Interaction Between LiCoO2 Thin Films and Adsorbed Water. J. Phys. Chem. C 2015, 119, 23407– 23412,  DOI: 10.1021/acs.jpcc.5b05793
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    22
    Photoemission Study on the Interaction Between LiCoO2 Thin Films and Adsorbed Water
    Motzko, M.; Carrillo Solano, M. A.; Jaegermann, W.; Hausbrand, R.
    Journal of Physical Chemistry C (2015), 119 (41), 23407-23412CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)
    Surface layers at the cathode-electrolyte interface strongly affect the performance of the Li-ion cell. Such surface layers are found during manufg. and operation of the battery. As water can never be fully excluded from the manufg. chain, it will form an addnl. surface layer situated between cathode and electrolyte. In this contribution, we investigate the interaction between the LiCoO2 electrode and H2O by a surface science approach. H2O was adsorbed stepwise onto a LiCoO2 thin film, and intermediate XPS anal. was performed after every step. Adsorption results in the formation of a Li2O/LiOH-type reaction layer on top of the electrode and downward band bending attributed to a Li+-ion transfer out of the electrode.
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  23. 23
    Cherkashinin, G.; Jaegermann, W. Dissociative Adsorption of H2O on LiCoO2(00l) Surfaces: Co Reduction Induced by Electron Transfer from Intrinsic Defects. J. Chem. Phys. 2016, 144, 184706,  DOI: 10.1063/1.4948610
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    23
    Dissociative adsorption of H2O on LiCoO2 (00l) surfaces: Co reduction induced by electron transfer from intrinsic defects
    Cherkashinin, G.; Jaegermann, W.
    Journal of Chemical Physics (2016), 144 (18), 184706/1-184706/7CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)
    Understanding the mechanism of the interaction of lithium ion conductors with water is crucial for both fundamental and technol. points of view. Despite the generally accepted fact that water is one of main sources of the degrdn. of Li-ion recharge batteries, the physicochem. processes occurring at the water-lithium ion conductor interface are not fully understood. By using synchrotron XPS (SXPS) and O K- and Co L- X-ray absorption near edge structure (XANES), we evidence that H2O is dissociatively adsorbed on LiCoO2 thin film at room temp. resulting in the formation of OH groups and the accumulation of the neg. charge at the surface accompanied by electron transfer to the initial empty Co3d (e*g) state. By considering the exptl. obtained energy diagram of the ionic conductor and water, direct charge transfer is not favorable due to a high difference in the chem. potential of the ionic conductor and electronic levels of the mol. Here, we develop the model for the dissociative water adsorption which explains the electron transfer to LiCoO2 by using the atomistic approach. The model takes into account the intrinsic defects found on the surface (<2 nm depth) by using the depth resolved photoemission expts. and can be explored to other layered transition metal oxides to interpret the interaction of water with the surface of ionic conductors. (c) 2016 American Institute of Physics.
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    Larcher, D.; Palacín, M. R.; Amatucci, G. G.; Tarascon, J. M. Electrochemically Active LiCoO2 and LiNiO2 Made by Cationic Exchange Under Hydrothermal Conditions. J. Electrochem. Soc. 1997, 144, 408– 417,  DOI: 10.1149/1.1837424
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    Electrochemically active LiCoO2 and LiNiO2 made by cationic exchange under hydrothermal conditions
    Larcher, D.; Palacin, M. R.; Amatucci, G. G.; Tarascon, J.-M.
    Journal of the Electrochemical Society (1997), 144 (2), 408-417CODEN: JESOAN; ISSN:0013-4651. (Electrochemical Society)
    The layered LiMO2 (M = Co, Ni) compds., which are of interest for Li-ion batteries, were synthesized at low temps. by hydrothermal treatment of LiOH·H2O aq. solns. contg. powd. HxMO2 phases. The reaction mechanism and the influence of temp., pressure, H2O diln. and precursor ratio on the ion exchange process, were studied. Single-phase LiMO2 can be obtained in 48 h at 160° at an air pressure of 60 bars from a MOOH/LiOH·H2O/H2O mixt. The progress of the exchange reaction for M = Co was monitored in situ using an autoclave which allowed sampling during the reaction. According to TEM and XRD studies the reaction occurs by surface H+-Li+ exchange and is accompanied by a progressive breaking of the particles due interfacial collapse. IR studies indicate that the LiCoO2 and LiNiO2 phases obtained are contaminated by carbonates that can be removed from LiCoO2 by washing with water followed by heating in vacuo at 200° for 2 days. When the ion-exchange parameters are controlled, the LiMO2 products exhibit an electrochem. performance comparable to that of high-temp. produced phases.
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  25. 25
    Mishra, K.; Pundir, S. S.; Rai, D. K. All-solid-state Proton Battery Using Gel Polymer Electrolyte. AIP Conf. Proc. 2014, 1591, 633,  DOI: 10.1063/1.4872700
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    All-solid-state proton battery using gel polymer electrolyte
    Mishra, Kuldeep; Pundir, S. S.; Rai, D. K.
    AIP Conference Proceedings (2014), 1591 (1, Solid State Physics), 633-635CODEN: APCPCS; ISSN:0094-243X. (American Institute of Physics)
    A proton conducting gel polymer electrolyte system; PMMA+NH4SCN+EC/PC, has been prepd. The highest ionic cond. obtained from the system is 2.5 × 10-4 S cm-1. The optimized compn. of the gel electrolyte has been used to fabricate a proton battery with Zn/ZnSO4·7H2O anode and MnO2 cathode. The open circuit voltage of the battery is 1.4 V and the highest energy d. is 5.7 W h kg-1 for low current drain. (c) 2014 American Institute of Physics.
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  26. 26
    Smith, J. P.; Brown, W. E.; Lehr, J. R. Structure of Crystalline Phosphoric Acid. J. Am. Chem. Soc. 1955, 77, 2728– 2730,  DOI: 10.1021/ja01615a013
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    Structure of crystalline phosphoric acid
    Smith, James P.; Brown, Walter E.; Lehr, James R.
    Journal of the American Chemical Society (1955), 77 (), 2728-30CODEN: JACSAT; ISSN:0002-7863.
    The crystal structure of anhyd. orthophosphoric acid was detd. by means of 2-dimension Fourier projections. The unit-cell dimensions are a = 5.80 ± 0.02, b = 4.85 ± 0.02, c = 11.62 ± 0.04 A., and angle β = 95°20' ± 20'. The space group is C52h-P21/c with 4 formula wts. of H3PO4 per unit cell. The lattice consts. of orthophosphoric acid hemihydrate are a = 7.94 ± 0.04, b = 12.94 ± 0.02, c = 7.38 ± 0.02 A., and angle β = 109°25' ± 30'. The space group is C52h-P21/a with 4 formula wts. of 2H3PO4.H2O per unit cell. The optical and morphological properties of the 2 cryst. forms of the acid are given.
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  27. 27
    Dippel, T.; Kreuer, K.; Lassegues, J.; Rodriguez, D. Proton Conductivity in Fused Phosphoric Acid; A 1H/31P PFG-NMR and QNS Study. Solid State Ionics 1993, 61, 41– 46,  DOI: 10.1016/0167-2738(93)90332-W
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    Proton conductivity in fused phosphoric acid; A 1H/31P PFG-NMR and QNS study
    Dippel, Th.; Kreuer, K. D.; Lassegues, J. C.; Rodriguez, D.
    Solid State Ionics (1993), 61 (1-3), 41-6CODEN: SSIOD3; ISSN:0167-2738.
    The self-diffusion coeffs. D(1H) and D(31P) for fused H3PO4 were measured by PFG (pulsed field gradient) NMR. The results are discussed together with cond., self-dissocn., and QNS (quasielastic neutron scattering) data. Conduction in H3PO4 appears to be predominately protonic (tH+ ≈ 0.975), and structure diffusion is proposed as the operating fast conduction and diffusion mechanism. There is an indication for correlated proton transfer.
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    Swift, M. W.; Qi, Y. First-principles Prediction of Potentials and Space-charge Layers in All-solid-state Batteries. Phys. Rev. Lett. 2019, 122, 167701  DOI: 10.1103/PhysRevLett.122.167701
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    First-Principles Prediction of Potentials and Space-Charge Layers in All-Solid-State Batteries
    Swift, Michael W.; Qi, Yue
    Physical Review Letters (2019), 122 (16), 167701pp.CODEN: PRLTAO; ISSN:1079-7114. (American Physical Society)
    As all-solid-state batteries (SSBs) develop as an alternative to traditional cells, a thorough theor. understanding of driving forces behind battery operation is needed. We present a fully first-principles-informed model of potential profiles in SSBs and apply the model to the Li/LiPON/LixCoO2 system. The model predicts interfacial potential drops driven by both electron transfer and Li+ space-charge layers that vary with the SSB's state of charge. The results suggest a lower electronic ionization potential in the solid electrolyte favors Li+ transport, leading to higher discharge power.
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    Neugebauer, J.; Van de Walle, C. G. Hydrogen in GaN: Novel Aspects of a Common Impurity. Phys. Rev. Lett. 1995, 75, 4452– 4455,  DOI: 10.1103/PhysRevLett.75.4452
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    Hydrogen in GaN: novel aspects of a common impurity
    Neugebauer, Jorg; Van de Walle, Chris G.
    Physical Review Letters (1995), 75 (24), 4452-5CODEN: PRLTAO; ISSN:0031-9007. (American Physical Society)
    The authors have studied electronic structure, energetics, and migration of H and H complexes in GaN, based on 1st-principles total-energy calcns. The calcns. reveal a no. of features very different from those exhibited by H in more traditional semiconductors such as Si or GaAs: a very large neg.-U effect (U ≈ 2.4 eV), the instability of the bond-center site, high energies for H mols., and an unusual geometry for the Mg-H complex. All of these features are a consequence of distinctive properties of GaN, namely, the strongly ionic nature and the large bond strength of the Ga-N bond. The authors propose a simple model for the neg.-U behavior, which should valid for H in any semiconductor.
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    Fingerle, M.; Buchheit, R.; Sicolo, S.; Albe, K.; Hausbrand, R. Reaction and Space Charge Layer Formation at the LiCoO2–LiPON Interface: Insights on Defect Formation and Ion Energy Level Alignment by a Combined Surface Science–Simulation Approach. Chem. Mater. 2017, 29, 7675– 7685,  DOI: 10.1021/acs.chemmater.7b00890
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    30
    Reaction and Space Charge Layer Formation at the LiCoO2-LiPON Interface: Insights on Defect Formation and Ion Energy Level Alignment by a Combined Surface Science-Simulation Approach
    Fingerle, Mathias; Buchheit, Roman; Sicolo, Sabrina; Albe, Karsten; Hausbrand, Rene
    Chemistry of Materials (2017), 29 (18), 7675-7685CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
    In this contribution, we investigate the formation and evolution of LiCoO2-LiPON interfaces upon annealing using photoelectron spectroscopy. We identify interlayer compds. related to the deposition process and study the chem. reactions leading to interlayer formation. Based on the structure of the pristine interface as well as on its evolution upon annealing, we relate reaction layer and space charge layer formation to chem. potential differences between the two materials. The results are discussed in terms of a combined Li-ion and electron interface energy level scheme providing insights into fundamental charge transfer processes. In constructing the energy level alignment, we take into account calcd. defect formation energies of lithium in the cathode and solid electrolyte.
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    Tukamoto, H.; West, A. R. Electronic Conductivity of LiCoO2 and Its Enhancement by Magnesium Doping. J. Electrochem. Soc. 1997, 144, 3164– 3168,  DOI: 10.1149/1.1837976
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    Electronic conductivity of LiCoO2 and its enhancement by magnesium doping
    Tukamoto, H.; West, A. R.
    Journal of the Electrochemical Society (1997), 144 (9), 3164-3168CODEN: JESOAN; ISSN:0013-4651. (Electrochemical Society)
    LiCoO2 the active cathode material in com. rechargeable lithium batteries, is shown to be a p-type semiconductor, assocd. with the presence of a small concn. of Co4+ ions. Its cond. at room temp. can be increased by over two order of magnitude, to ∼0.5 S cm-1, by partial substitution of Co3+ by Mg2+ and compensating hole creation. The electrochem. performance of LiMg0.05Co0.95O2 is comparable to that of LiCoO2; a small redn. in capacity, assocd. with a redn. in Co3+ content, occurs but good reversibility is retained and, in contrast to LiCoO2, the Mg-doped material is single phase throughout the charge/discharge cycle.
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    Momma, K.; Izumi, F. VESTA 3 for Three-dimensional Visualization of Crystal, Volumetric and Morphology Data. J. Appl. Crystallogr. 2011, 44, 1272– 1276,  DOI: 10.1107/S0021889811038970
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    VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data
    Momma, Koichi; Izumi, Fujio
    Journal of Applied Crystallography (2011), 44 (6), 1272-1276CODEN: JACGAR; ISSN:0021-8898. (International Union of Crystallography)
    VESTA is a 3D visualization system for crystallog. studies and electronic state calcns. It was upgraded to the latest version, VESTA 3, implementing new features including drawing the external morphpol. of crysals; superimposing multiple structural models, volumetric data and crystal faces; calcn. of electron and nuclear densities from structure parameters; calcn. of Patterson functions from the structure parameters or volumetric data; integration of electron and nuclear densities by Voronoi tessellation; visualization of isosurfaces with multiple levels, detn. of the best plane for selected atoms; an extended bond-search algorithm to enable more sophisticated searches in complex mols. and cage-like structures; undo and redo is graphical user interface operations; and significant performance improvements in rendering isosurfaces and calcg. slices.
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    Van de Walle, C. G.; Neugebauer, J. Universal Alignment of Hydrogen Levels in Semiconductors, Insulators and Solutions. Nature 2003, 423, 626– 628,  DOI: 10.1038/nature01665
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    Universal alignment of hydrogen levels in semiconductors, insulators and solutions
    Van de Walle, Chris G.; Neugebauer, J.
    Nature (London, United Kingdom) (2003), 423 (6940), 626-628CODEN: NATUAS; ISSN:0028-0836. (Nature Publishing Group)
    Hydrogen strongly affects the electronic and structural properties of many materials. It can bind to defects or to other impurities, often eliminating their elec. activity: this effect of defect passivation is crucial to the performance of many photovoltaic and electronic devices. A fuller understanding of hydrogen in solids is required to support development of improved hydrogen-storage systems, proton-exchange membranes for fuel cells, and high-permittivity dielecs. for integrated circuits. In chem. and in biol. systems, there also were many efforts to correlate proton affinity and deprotonation with host properties. Here the authors report a systematic theor. study (based on ab initio methods) of hydrogen in a wide range of hosts, which reveals the existence of a universal alignment for the electronic transition level of hydrogen in semiconductors, insulators and even aq. solns. This alignment allows the prediction of the elec. activity of hydrogen in any host material once some basic information about the band structure of that host is known. The authors present a phys. explanation that connects the behavior of hydrogen to the line-up of electronic band structures at heterojunctions.
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    Xu, G.; Li, J.; Wang, C.; du, X.; Lu, D.; Xie, B.; Wang, X.; Lu, C.; Liu, H.; Dong, S.; Cui, G.; Chen, L. The Formation/Decomposition Equilibrium of LiH and Its Contribution on Anode Failure in Practical Lithium Metal Batteries. Angew. Chem., Int. Ed. 2021, 60, 7770– 7776,  DOI: 10.1002/anie.202013812
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    The Formation/Decomposition Equilibrium of LiH and its Contribution on Anode Failure in Practical Lithium Metal Batteries
    Xu, Gaojie; Li, Jiedong; Wang, Chao; Du, Xiaofan; Lu, Di; Xie, Bin; Wang, Xiao; Lu, Chenglong; Liu, Haisheng; Dong, Shanmu; Cui, Guanglei; Chen, Liquan
    Angewandte Chemie, International Edition (2021), 60 (14), 7770-7776CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
    Discovering the underlying reason for Li anode failure is a crit. step towards applications of lithium metal batteries (LMBs). In this work, we conduct deuterium-oxide (D2O) titrn. expts. in a novel online gas anal. mass spectrometry (MS) system, to det. the content of metallic Li and lithium hydride (LiH) in cycled Li anodes disassembled from practical LiCoO2/Li LMBs. The practical cell is comprised of ultrathin Li anode (50 μm), high loading LiCoO2 (17 mg cm-2, 2.805 mAh cm-2) and different formulated electrolytes. Our results suggest that the amt. of LiH accumulation is neg. correlated with cyclability of practical LMBs. More importantly, we reveal a temp. sensitive equil. (Li + 1/2 H2 .dblharw. LiH) governing formation and decompn. process of LiH at Li anode. We believe that the unusual understanding provided by this study will draw forth more insightful efforts to realize efficient Li protection and the ultimate applications of "holy grail" LMBs.
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  • Abstract

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    Figure 1

    Figure 1. Electrochemical characteristics of the (a, c, and e) in vacuo and (b, d, and f) air-exposed batteries. cyclic voltammetry (CV) curves of the (a) in vacuo and (b) air-exposed batteries. The voltage was swept at a rate of 1 mV·s–1 from 3.0 to 4.3 V vs Li+/Li. The displayed curves correspond to the 20th charge–discharge cycle. Impedance spectra of the (c) in vacuo and (d) air-exposed batteries recorded at voltages of 3.8 and 4.2 V vs Li+/Li. The numbers n in the plots indicate frequencies (10n Hz). Low-frequency regions of the impedance spectra recorded for the (e) in vacuo and (f) air-exposed batteries. The fitting data obtained for the equivalent circuit at 4.2 V vs Li+/Li data (Table S1) are shown as colored semicircles. The light-green semicircle denotes the resistance of Li ion conduction in the Li3PO4 solid electrolyte. The gray semicircle represents the Li3PO4–LiCoO2 interface resistance (10.9 Ω·cm2 for the in vacuo battery and 200 Ω·cm2 for the air-exposed battery).

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    Figure 2

    Figure 2. (a) CV curves of the H2O-vapor-exposed battery recorded before (blue) and after (red) annealing in an Ar atmosphere at a temperature of 150 °C and pressure of 1 atm for 60 min. The measurements were conducted after the samples had been cooled down to ambient temperature. The voltage was swept in the range from 3.0 to 4.3 V vs Li/Li+ at a rate of 1 mV·s–1. (b) Impedance spectra recorded at voltages of 3.8 and 4.2 V vs Li+/Li for the H2O-vapor-exposed battery after annealing. The numbers denote the frequencies. (c) Dependence of the interface resistance on the annealing time obtained at a voltage of 4.2 V vs Li+/Li and an annealing temperature of 150 °C. The interface resistances were measured after cooling the sample to room temperature (27 °C). (d) Annealing temperature dependences of the interface resistance obtained at a voltage 4.2 V vs Li+/Li and annealing times of 60 and 120 min.

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    Figure 3

    Figure 3. (a) X-ray crystal truncation rod (CTR) scattering profiles of the pristine (in vacuo, black), H2O-vapor-exposed (blue), and annealed (red) battery samples. The spectra were recorded after depositing Li3PO4 layers on the LiCoO2 surfaces. An Li thin film was deposited only on the Li3PO4 layer of the annealed battery sample. The thicknesses of the LiCoO2, Li3PO4, and Li thin films were 5 nm, 500 nm, and 1 μm, respectively. (b) Electron density profiles of the in vacuo, H2O-vapor-exposed, and annealed battery samples derived from the results of structural analyses of the corresponding CTR profiles. Owing to the existence of the antiphase domain, the electron density of the Li layer appears to be larger than the actual electron density of Li.

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    Figure 4

    Figure 4. (a) Left: optimized crystal structure of the bulk LiCoO2 unit cell with an interstitial H atom. Right: schematic of H–O bonding at the most stable site. The adjacent Li atom is shifted from the O and H atoms. The structures were visualized using the VESTA software package. (33) (b) Formation energies of the neutral and charged H interstitials in the bulk LiCoO2 structures plotted as functions of the Fermi energy (EF) with respect to the valence-band maximum. The H partial pressure was set to pH2 ≈ 10–9 atm. The kinks correspond to the (+/0) charge transition levels. (c) Energy diagram constructed for the diffusion of an interstitial H from the most stable site to the closest neighboring stable site. The activation energy (Eact) of the proton diffusion process was estimated by considering the zero-point energies of the initial and transition states. (d) Diffusion coefficients estimated for an interstitial H atom in the LiCoO2 structure at different annealing temperatures.

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    Figure 5

    Figure 5. (a–c) Negative ion time-of-flight secondary ion mass spectroscopy spectra for OH–, Al–, P–, and Co–. Figure S10 presents the data for Li– and H–. The green and blue regions represent Li3PO4 and LiCoO2, respectively. The signals of Al–, P–, and Co– were used to identify the interfaces. (a) Sample without H2O exposure, (b) H2O-vapor-exposed battery, and (c) battery annealed after H2O vapor exposure. An Li layer was deposited on the annealed sample only. (d) Schematic illustration of the battery performance deterioration with a large interface resistance caused by water adsorption and recovery of the low interface resistance via battery annealing.

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      Issues and challenges facing rechargeable lithium batteries
      Tarascon, J.-M.; Armand, M.
      Nature (London, United Kingdom) (2001), 414 (6861), 359-367CODEN: NATUAS; ISSN:0028-0836. (Nature Publishing Group)
      A review of the development of lithium-based rechargeable batteries. Ongoing research strategies are highlighted, and the challenges that remain regarding the synthesis, characterization, electrochem. performance, and safety of these systems are discussed.
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    2. 2
      Manthiram, A.; Yu, X.; Wang, S. Lithium Battery Chemistries Enabled by Solid-state Electrolytes. Nat. Rev. Mater. 2017, 2, 16103,  DOI: 10.1038/natrevmats.2016.103
      2
      Lithium battery chemistries enabled by solid-state electrolytes
      Manthiram, Arumugam; Yu, Xingwen; Wang, Shaofei
      Nature Reviews Materials (2017), 2 (3), 16103CODEN: NRMADL; ISSN:2058-8437. (Nature Publishing Group)
      Solid-state electrolytes are attracting increasing interest for electrochem. energy storage technologies. In this Review, we provide a background overview and discuss the state of the art, ion-transport mechanisms and fundamental properties of solid-state electrolyte materials of interest for energy storage applications. We focus on recent advances in various classes of battery chemistries and systems that are enabled by solid electrolytes, including all-solid-state lithium-ion batteries and emerging solid-electrolyte lithium batteries that feature cathodes with liq. or gaseous active materials (for example, lithium-air, lithium-sulfur and lithium-bromine systems). A low-cost, safe, aq. electrochem. energy storage concept with a 'mediator-ion' solid electrolyte is also discussed. Advanced battery systems based on solid electrolytes would revitalize the rechargeable battery field because of their safety, excellent stability, long cycle lives and low cost. However, great effort will be needed to implement solid-electrolyte batteries as viable energy storage systems. In this context, we discuss the main issues that must be addressed, such as achieving acceptable ionic cond., electrochem. stability and mech. properties of the solid electrolytes, as well as a compatible electrolyte/electrode interface.
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    3. 3
      Wu, J.; Shen, L.; Zhang, Z.; Liu, G.; Wang, Z.; Zhou, D.; Wan, H.; Xu, X.; Yao, X. All-Solid-State Lithium Batteries with Sulfide Electrolytes and Oxide Cathodes. Electrochem. Energy Rev. 2021, 4, 101– 135,  DOI: 10.1007/s41918-020-00081-4
      3
      All-Solid-State Lithium Batteries with Sulfide Electrolytes and Oxide Cathodes
      Wu, Jinghua; Shen, Lin; Zhang, Zhihua; Liu, Gaozhan; Wang, Zhiyan; Zhou, Dong; Wan, Hongli; Xu, Xiaoxiong; Yao, Xiayin
      Electrochemical Energy Reviews (2021), 4 (1), 101-135CODEN: EERLAM; ISSN:2520-8136. (Springer International Publishing AG)
      A review. All-solid-state lithium batteries (ASSLBs) have attracted increasing attention due to their high safety and energy d. Among all corresponding solid electrolytes, sulfide electrolytes are considered to be the most promising ion conductors due to high ionic conductivities. Despite this, many challenges remain in the application of ASSLBs, including the stability of sulfide electrolytes, complex interfacial issues between sulfide electrolytes and oxide electrodes as well as unstable anodic interfaces. Although oxide cathodes remain the most viable electrode materials due to high stability and industrialization degrees, the matching of sulfide electrolytes with oxide cathodes is challenging for com. use in ASSLBs. Based on this, this review will present an overview of emerging ASSLBs based on sulfide electrolytes and oxide cathodes and highlight crit. properties such as compatible electrolyte/electrode interfaces. And by considering the current challenges and opportunities of sulfide electrolyte-based ASSLBs, possible research directions and perspectives are discussed.
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    4. 4
      Wu, J.; Sufu, L.; Han, F.; Yao, X.; Wang, C. Lithium/Sulfide All-Solid-State Batteries using Sulfide Electrolytes. Adv. Mater. 2020, 33, 2000751  DOI: 10.1002/adma.202000751
      There is no corresponding record for this reference.
    5. 5
      Tan, D. H. S.; Chen, Y.; Yang, H.; Bao, W.; Sreenarayanan, B.; Doux, J.; Li, W.; Lu, B.; Ham, S.; Sayahpour, B.; Scharf, J.; Wu, E. A.; Deysher, G.; Han, H. E.; Hah, H. J.; Jeong, H.; Lee, J. B.; Chen, Z.; Meng, Y. S. Carbon-free high-loading silicon anodes enabled by sulfide solid electrolytes. Science 2021, 373, 1494– 1499,  DOI: 10.1126/science.abg7217
      5
      Carbon-free high-loading silicon anodes enabled by sulfide solid electrolytes
      Tan, Darren H. S.; Chen, Yu-Ting; Yang, Hedi; Bao, Wurigumula; Sreenarayanan, Bhagath; Doux, Jean-Marie; Li, Weikang; Lu, Bingyu; Ham, So-Yeon; Sayahpour, Baharak; Scharf, Jonathan; Wu, Erik A.; Deysher, Grayson; Han, Hyea Eun; Hah, Hoe Jin; Jeong, Hyeri; Lee, Jeong Beom; Chen, Zheng; Meng, Ying Shirley
      Science (Washington, DC, United States) (2021), 373 (6562), 1494-1499CODEN: SCIEAS; ISSN:1095-9203. (American Association for the Advancement of Science)
      The development of silicon anodes for lithium-ion batteries has been largely impeded by poor interfacial stability against liq. electrolytes. Here, we enabled the stable operation of a 99.9 wt. % microsilicon anode by using the interface passivating properties of sulfide solid electrolytes. Bulk and surface characterization, and quantification of interfacial components, showed that such an approach eliminates continuous interfacial growth and irreversible lithium losses. Microsilicon full cells were assembled and found to achieve high areal c.d., wide operating temp. range, and high areal loadings for the different cells. The promising performance can be attributed to both the desirable interfacial property between microsilicon and sulfide electrolytes and the distinctive chemomech. behavior of the lithium-silicon alloy.
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    6. 6
      Yamada, H.; Tsunoe, D.; Shiraishi, S.; Isomichi, G. Reduced Grain Boundary Resistance by Surface Modification. J. Phys. Chem. C 2015, 119, 5412– 5419,  DOI: 10.1021/jp510077z
      6
      Reduced Grain Boundary Resistance by Surface Modification
      Yamada, Hirotoshi; Tsunoe, Daisuke; Shiraishi, Shota; Isomichi, Gakuho
      Journal of Physical Chemistry C (2015), 119 (10), 5412-5419CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)
      Interfacial resistance is one of the severe problems in composite electrodes of all solid state batteries (ASSBs), esp. oxide-type ASSBs. Conflicts between poor sinterability and possible unfavorable reaction with active materials limit applicable materials and processes. A novel approach probably decreases grain boundary resistance among nonsintered solid electrolyte particles. The concept is successfully demonstrated, and the nonsintered grain boundary resistance of a highly conducting solid electrolyte (Li1.3Al0.3Ti1.7(PO4)3) was suppressed by being coated with poorly conducting solid electrolyte (Li2SiO3). Increased total cond. and variation of apparent activation energy are well explained from the viewpoint of defect chem.
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    7. 7
      Gittleson, F. S.; el Gabaly, F. Non-faradaic Li+ Migration and Chemical Coordination Across Solid-state Battery Interfaces. Nano Lett. 2017, 17, 6974– 6982,  DOI: 10.1021/acs.nanolett.7b03498
      7
      Non-Faradaic Li+ Migration and Chemical Coordination across Solid-State Battery Interfaces
      Gittleson, Forrest S.; El Gabaly, Farid
      Nano Letters (2017), 17 (11), 6974-6982CODEN: NALEFD; ISSN:1530-6984. (American Chemical Society)
      Efficient and reversible charge transfer is essential to realizing high-performance solid-state batteries. Efforts to enhance charge transfer at crit. electrode-electrolyte interfaces have proven successful, yet interfacial chem. and its impact on cell function remains poorly understood. Using XPS combined with electrochem. techniques, we elucidate chem. coordination near the LiCoO2-LIPON interface, providing exptl. validation of space-charge sepn. Space-charge layers, defined by local enrichment and depletion of charges, have previously been theorized and modeled, but the unique chem. of solid-state battery interfaces is now revealed. Here we highlight the non-Faradaic migration of Li+ ions from the electrode to the electrolyte, which reduces reversible cathodic capacity by ∼15%. Inserting a thin, ion-conducting LiNbO3 interlayer between the electrode and electrolyte, however, can reduce space-charge sepn., mitigate the loss of Li+ from LiCoO2, and return cathodic capacity to its theor. value. This work illustrates the importance of interfacial chem. in understanding and improving solid-state batteries.
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    8. 8
      Yada, C.; Ohmori, A.; Ide, K.; Yamasaki, H.; Kato, T.; Saito, T.; Sagane, F.; Iriyama, Y. Dielectric Modification of 5V-class Cathodes for High-voltage All-solid-state Lithium Batteries. Adv. Energy Mater. 2014, 4, 1301416  DOI: 10.1002/aenm.201301416
      There is no corresponding record for this reference.
    9. 9
      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
      9
      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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    10. 10
      Zhang, W.; Richter, F. H.; Culver, S. P.; Leichtweiss, T.; Lozano, J. G.; Dietrich, C.; Bruce, P. G.; Zeier, W. G.; Janek, J. Degradation Mechanisms at the Li10GeP2S12/LiCoO2 Cathode Interface in an All-solid-state Lithium-ion Battery. ACS Appl. Mater. Interfaces 2018, 10, 22226– 22236,  DOI: 10.1021/acsami.8b05132
      10
      Degradation mechanisms at the Li10GeP2S12/LiCoO2 cathode interface in an all-solid-state lithium-ion battery
      Zhang, Wenbo; Richter, Felix H.; Culver, Sean P.; Leichtweiss, Thomas; Lozano, Juan G.; Dietrich, Christian; Bruce, Peter G.; Zeier, Wolfgang G.; Janek, Juergen
      ACS Applied Materials & Interfaces (2018), 10 (26), 22226-22236CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
      All-solid-state batteries (ASSBs) show great potential for providing high power and energy densities with enhanced battery safety. While new solid electrolytes (SEs) have been developed with high enough ionic conductivities, SSBs with long operational life are still rarely reported. Therefore, on the way to high-performance and long-life ASSBs, a better understanding of the complex degrdn. mechanisms, occurring at the electrode/electrolyte interfaces is pivotal. While the lithium metal/solid electrolyte interface is receiving considerable attention due to the quest for high energy d., the interface between the active material and solid electrolyte particles within the composite cathode is arguably the most difficult to solve and study. In this work, multiple characterization methods are combined to better understand the processes that occur at the LiCoO2 cathode and the Li10GeP2S12 solid electrolyte interface. Indium and Li4Ti5O12 are used as anode materials to avoid the instability problems assocd. with Li-metal anodes. Capacity fading and increased impedances are obsd. during long-term cycling. Postmortem anal. with scanning transmission electron microscopy, electron energy loss spectroscopy, x-ray diffraction, and XPS show that electrochem. driven mech. failure and degrdn. at the cathode/solid electrolyte interface contribute to the increase in internal resistance and the resulting capacity fading. These results suggest that the development of electrochem. more stable SEs and the engineering of cathode/SE interfaces are crucial for achieving reliable SSB performance.
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    11. 11
      Iriyama, Y.; Kako, T.; Yada, C.; Abe, T.; Ogumi, Z. Reduction of Charge Transfer Resistance at the Lithium Phosphorus Oxynitride/Lithium Cobalt Oxide Interface by Thermal Treatment. J. Power Sources 2005, 146, 745– 748,  DOI: 10.1016/j.jpowsour.2005.03.073
      11
      Reduction of charge transfer resistance at the lithium phosphorus oxynitride/lithium cobalt oxide interface by thermal treatment
      Iriyama, Yasutoshi; Kako, Tomonori; Yada, Chihiro; Abe, Takeshi; Ogumi, Zempachi
      Journal of Power Sources (2005), 146 (1-2), 745-748CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)
      An all-solid-state thin-film battery consisting of a c-axis-oriented LiCoO2 thin-film and a Li P oxynitride (LiPON) glass electrolyte was fabricated. Heat treatment at 473 K after fabrication of the LiPON/LiCoO2 interface decreased the charge transfer resistance at the interface, and the resistance was further decreased by prolonging the treatment time. The charge transfer resistance per unit electrode area (interfacial resistivity) of a film battery, heat-treated for 60 min, decreased to 125 Ω·cm2, which is ∼5 times larger than that of the ref. system: 1M LiClO4 dissolved in propylene carbonate/LiCoO2 interface - 25 Ω·cm2. Due to the decrease in charge transfer resistance at the LiPON/LiCoO2 interface, the reaction current of the film battery increased due to the heat treatment. Heat-treated film batteries had stable electrochem. Li insertion/extn. properties compared with batteries using conventional org. electrolytes. Voltammograms and the impedance spectra of the film battery maintained their initial shape for over 100 cycles, and the capacity retention ratio per cycle was 99.9%.
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    12. 12
      Iriyama, Y.; Kako, T.; Yada, C.; Abe, T.; Ogumi, Z. Charge Transfer Reaction at the Lithium Phosphorus Oxynitride Glass Electrolyte/Lithium Cobalt Oxide Thin Film Interface. Solid State Ionics 2005, 176, 2371– 2376,  DOI: 10.1016/j.ssi.2005.02.025
      12
      Charge transfer reaction at the lithium phosphorus oxynitride glass electrolyte/lithium cobalt oxide thin film interface
      Iriyama, Yasutoshi; Kako, Tomonori; Yada, Chihiro; Abe, Takeshi; Ogumi, Zempachi
      Solid State Ionics (2005), 176 (31-34), 2371-2376CODEN: SSIOD3; ISSN:0167-2738. (Elsevier B.V.)
      An all-solid-state thin film battery consisting of a c-axis-oriented LiCoO2 thin film and a lithium phosphorus oxynitride (LiPON) glass electrolyte was fabricated, and the charge transfer reaction at the LiPON/LiCoO2 interface was studied. Thermal treatment at 473 °K after the formation of the LiPON/LiCoO2 interface improved the reactivity of the film battery, in good agreement with the result previously reported. This improvement was predominantly due to a redn. in charge transfer resistance at the LiPON/LiCoO2 interface. The activation energy of the charge transfer reaction did not change as a result of thermal treatment, indicating that the redn. was not caused by a decrease in activation energy. Because thermal treatment induced a change in chem. bonding in the LiPON film, probably these structural changes induced some modification at the LiPON/LiCoO2 interface, which resulted in an increase in the no. of electrochem. active sites in the contact area.
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    13. 13
      Faenza, N. V.; Bruce, L.; Lebens-Higgins, Z. W.; Plitz, I.; Pereira, N.; Piper, L. F.; Amatucci, G. G. Growth of Ambient Induced Surface Impurity Species on Layered Positive Electrode Materials and Impact on Electrochemical Performance. J. Electrochem. Soc. 2017, 164, A3727– A3741,  DOI: 10.1149/2.0921714jes
      13
      Growth of Ambient Induced Surface Impurity Species on Layered Positive Electrode Materials and Impact on Electrochemical Performance
      Faenza, Nicholas V.; Bruce, Lejandro; Lebens-Higgins, Zachary W.; Plitz, Irene; Pereira, Nathalie; Piper, Louis F. J.; Amatucci, Glenn G.
      Journal of the Electrochemical Society (2017), 164 (14), A3727-A3741CODEN: JESOAN; ISSN:0013-4651. (Electrochemical Society)
      Surface impurity species, most notably Li2CO3, that develop on layered oxide pos. electrode materials with atm. aging have been reported to be highly detrimental to the subsequent electrochem. performance. LiNi0.8Co0.15Al0.05O2 (NCA) was used as a model layered oxide compd. to evaluate the growth and subsequent electrochem. impact of H2O, LiHCO3, LiOH and Li2CO3. Methodical high temp. annealing enabled the systematic removal of each impurity specie, thus permitting the detn. of each specie's individual effect on the host material's electrochem. performance. Extensive cycling of exposed and annealed materials emphasized the cycle life degrdn. and capacity loss induced by each impurity, while rate capability measurements correlated the electrode impedance to the impurity species present. Based on these characterization results, this work attempts to clarify decades of ambiguity over the growth mechanisms and the electrochem. impact of the sp. surface impurity species formed during powder storage in various environments.
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    14. 14
      Sicklinger, J.; Metzger, M.; Beyer, H.; Pritzl, D.; Gasteiger, H. A. Ambient Storage Derived Surface Contamination of NCM811 and NCM111: Performance Implications and Mitigation Strategies. J. Electrochem. Soc. 2019, 166, A2322– A2335,  DOI: 10.1149/2.0011912jes
      14
      Ambient storage derived surface contamination of NCM811 and NCM111: performance implications and mitigation strategies
      Sicklinger, Johannes; Metzger, Michael; Beyerz, Hans; Pritzl, Daniel; Gasteiger, Hubert A.
      Journal of the Electrochemical Society (2019), 166 (12), A2322-A2335CODEN: JESOAN; ISSN:0013-4651. (Electrochemical Society)
      The quality of metal oxide-based battery active materials is compromised by surface contamination from storage and handling at ambient conditions. We present a detailed anal. of the true nature and the quantity of the surface contaminants on two different cathode active materials, the widely used LiNi1/3Co1/3Mn1/3O2 (NCM111) and the Ni-rich LiNi0.8Co0.1Mn0.1O2 (NCM811). We process these materials in three distinct conditions "wet" (excessive exposure to moisture), "dry" (std. drying of as-received materials), and "calcined" (heat-treatment of cathode powders). Surface contaminants are then quantified by thermogravimetric anal. coupled with mass spectrometry (TGA-MS), and their reactivity with an ethylene carbonate-based electrolyte is evaluated using online mass spectrometry (OMS). We demonstrate that not only the commonly assumed LiOH and Li2CO3 residues account for NCM performance deterioration upon storage in moisture and CO2 contg. atm., but also basic transition metal hydroxides/carbonates formed on the material surface. Eventually, we showcase a thermal treatment that removes these transition metal based surface contaminants and leads to superior cycling stability.
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    15. 15
      Takada, K.; Ohta, N.; Zhang, L.; Fukuda, K.; Sakaguchi, I.; 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
      15
      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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    16. 16
      Han, F.; Yue, J.; Chen, C.; Zhao, N.; Fan, X.; Ma, Z.; Gao, T.; Wang, F.; Guo, X.; Wang, C. Interphase engineering enabled all-ceramic lithium battery. Joule 2018, 2, 497– 508,  DOI: 10.1016/j.joule.2018.02.007
      16
      Interphase Engineering Enabled All-Ceramic Lithium Battery
      Han, Fudong; Yue, Jie; Chen, Cheng; Zhao, Ning; Fan, Xiulin; Ma, Zhaohui; Gao, Tao; Wang, Fei; Guo, Xiangxin; Wang, Chunsheng
      Joule (2018), 2 (3), 497-508CODEN: JOULBR; ISSN:2542-4351. (Cell Press)
      Solid-state batteries (SSBs) can essentially improve battery safety. Garnet-type Li7La3Zr2O12 (LLZO) is considered one of the most promising solid electrolytes for SSBs. However, the performance of LLZO-based SSBs is limited by the large cathode/electrolyte interfacial resistance. High-rate and long-cycling SSBs were achieved only after adding flammable polymer or liq. electrolyte in the cathode at the sacrifice of safety. Here, we show that an all-ceramic cathode/electrolyte with an extremely low interfacial resistance can be realized by thermally soldering LiCoO2 (LCO) and LLZO together with the Li2.3-xC0.7+xB0.3-xO3 solid electrolyte interphase through the reaction between the Li2.3C0.7B0.3O3 solder and the Li2CO3 layers that can be conformally coated on both LLZO and LCO. The all-solid-state Li/LLZO/LCO battery with such an all-ceramic cathode/electrolyte exhibits high cycling stability and high rate performance, constituting a significant step toward the practical applications of SSBs.
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    17. 17
      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
      17
      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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    18. 18
      Kuwata, N.; Iwagami, N.; Tanji, Y.; Matsuda, Y.; Kawamura, J. Characterization of Thin-film Lithium Batteries with Stable Thin-film Li3PO4 Solid Electrolytes Fabricated by ArF Excimer Laser Deposition. J. Electrochem. Soc. 2010, 157, A521– A527,  DOI: 10.1149/1.3306339
      18
      Characterization of Thin-Film Lithium Batteries with Stable Thin-Film Li3PO4 Solid Electrolytes Fabricated by ArF Excimer Laser Deposition
      Kuwata, Naoaki; Iwagami, Naoya; Tanji, Yoshinari; Matsuda, Yasutaka; Kawamura, Junichi
      Journal of the Electrochemical Society (2010), 157 (4), A521-A527CODEN: JESOAN; ISSN:0013-4651. (Electrochemical Society)
      High quality Li3PO4 thin films have been prepd. by pulsed laser deposition (PLD) as a solid electrolyte for thin-film batteries. The structure, compn., ionic cond., and electrochem. stability of the Li3PO4 thin films have been characterized. The Li3PO4 film exhibits a single lithium-ion conductor with an ionic cond. of 4.0 × 10-7 S/cm at 25° and an activation energy of 0.58 eV. The Li3PO4 film is electrochem. stable in the potential range 0-4.7 V vs. Li/Li+. All-solid-state thin-film batteries, Li/Li3PO4/LiCoO2, have been fabricated by using PLD-grown Li3PO4 thin film. The thin-film battery shows excellent intercalation property and stability for long-term cycling in the potential range 3.0-4.4 V.
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    19. 19
      Garcia, B.; Farcy, J.; Pereira-Ramos, J. P.; Baffier, N. Electrochemical Properties of Low Temperature Crystallized LiCoO2. J. Electrochem. Soc. 1997, 114, 1179– 1184
      There is no corresponding record for this reference.
    20. 20
      Bates, J. B.; Dudney, N. J.; Gruzalski, G. R.; Zuhr, R. A.; Choudhury, A.; Luck, C. 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
      20
      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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    21. 21
      Zou, L.; He, Y.; Liu, Z.; Jia, H.; Zhu, J.; Zheng, J.; Wang, G.; Li, X.; Xiao, J.; Liu, J.; Zhang, J. G.; Chen, G.; Wang, C. Unlocking the Passivation Nature of the Cathode–Air Interfacial Reactions in Lithium Ion Batteries. Nat. Commun. 2020, 11, 3204,  DOI: 10.1038/s41467-020-17050-6
      21
      Unlocking the passivation nature of the cathode-air interfacial reactions in lithium ion batteries
      Zou, Lianfeng; He, Yang; Liu, Zhenyu; Jia, Haiping; Zhu, Jian; Zheng, Jianming; Wang, Guofeng; Li, Xiaolin; Xiao, Jie; Liu, Jun; Zhang, Ji-Guang; Chen, Guoying; Wang, Chongmin
      Nature Communications (2020), 11 (1), 3204CODEN: NCAOBW; ISSN:2041-1723. (Nature Research)
      It is classically well perceived that cathode-air interfacial reactions, often instantaneous and thermodn. non-equil., will lead to the formation of interfacial layers, which subsequently, often vitally, control the behavior and performance of batteries. However, understanding of the nature of cathode-air interfacial reactions remain elusive. Here, using at.-resoln., time-resolved in-situ environmental transmission electron microscopy and atomistic simulation, we reveal that the cathode-water interfacial reactions can lead to the surface passivation, where the resultant conformal LiOH layers present a crit. thickness beyond which the otherwise sustained interfacial reactions are arrested. We rationalize that the passivation behavior is dictated by the Li+-water interaction driven Li-ion de-intercalation, rather than a direct cathode-gas chem. reaction. Further, we show that a thin disordered rock salt layer formed on the cathode surface can effectively mitigate the surface degrdn. by suppressing chem. delithiation. The established passivation paradigm opens new venues for the development of novel high-energy and high-stability cathodes.
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    22. 22
      Motzko, M.; Carrillo Solano, M. A.; Jaegermann, W.; Hausbrand, R. Photoemission Study on the Interaction Between LiCoO2 Thin Films and Adsorbed Water. J. Phys. Chem. C 2015, 119, 23407– 23412,  DOI: 10.1021/acs.jpcc.5b05793
      22
      Photoemission Study on the Interaction Between LiCoO2 Thin Films and Adsorbed Water
      Motzko, M.; Carrillo Solano, M. A.; Jaegermann, W.; Hausbrand, R.
      Journal of Physical Chemistry C (2015), 119 (41), 23407-23412CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)
      Surface layers at the cathode-electrolyte interface strongly affect the performance of the Li-ion cell. Such surface layers are found during manufg. and operation of the battery. As water can never be fully excluded from the manufg. chain, it will form an addnl. surface layer situated between cathode and electrolyte. In this contribution, we investigate the interaction between the LiCoO2 electrode and H2O by a surface science approach. H2O was adsorbed stepwise onto a LiCoO2 thin film, and intermediate XPS anal. was performed after every step. Adsorption results in the formation of a Li2O/LiOH-type reaction layer on top of the electrode and downward band bending attributed to a Li+-ion transfer out of the electrode.
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    23. 23
      Cherkashinin, G.; Jaegermann, W. Dissociative Adsorption of H2O on LiCoO2(00l) Surfaces: Co Reduction Induced by Electron Transfer from Intrinsic Defects. J. Chem. Phys. 2016, 144, 184706,  DOI: 10.1063/1.4948610
      23
      Dissociative adsorption of H2O on LiCoO2 (00l) surfaces: Co reduction induced by electron transfer from intrinsic defects
      Cherkashinin, G.; Jaegermann, W.
      Journal of Chemical Physics (2016), 144 (18), 184706/1-184706/7CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)
      Understanding the mechanism of the interaction of lithium ion conductors with water is crucial for both fundamental and technol. points of view. Despite the generally accepted fact that water is one of main sources of the degrdn. of Li-ion recharge batteries, the physicochem. processes occurring at the water-lithium ion conductor interface are not fully understood. By using synchrotron XPS (SXPS) and O K- and Co L- X-ray absorption near edge structure (XANES), we evidence that H2O is dissociatively adsorbed on LiCoO2 thin film at room temp. resulting in the formation of OH groups and the accumulation of the neg. charge at the surface accompanied by electron transfer to the initial empty Co3d (e*g) state. By considering the exptl. obtained energy diagram of the ionic conductor and water, direct charge transfer is not favorable due to a high difference in the chem. potential of the ionic conductor and electronic levels of the mol. Here, we develop the model for the dissociative water adsorption which explains the electron transfer to LiCoO2 by using the atomistic approach. The model takes into account the intrinsic defects found on the surface (<2 nm depth) by using the depth resolved photoemission expts. and can be explored to other layered transition metal oxides to interpret the interaction of water with the surface of ionic conductors. (c) 2016 American Institute of Physics.
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    24. 24
      Larcher, D.; Palacín, M. R.; Amatucci, G. G.; Tarascon, J. M. Electrochemically Active LiCoO2 and LiNiO2 Made by Cationic Exchange Under Hydrothermal Conditions. J. Electrochem. Soc. 1997, 144, 408– 417,  DOI: 10.1149/1.1837424
      24
      Electrochemically active LiCoO2 and LiNiO2 made by cationic exchange under hydrothermal conditions
      Larcher, D.; Palacin, M. R.; Amatucci, G. G.; Tarascon, J.-M.
      Journal of the Electrochemical Society (1997), 144 (2), 408-417CODEN: JESOAN; ISSN:0013-4651. (Electrochemical Society)
      The layered LiMO2 (M = Co, Ni) compds., which are of interest for Li-ion batteries, were synthesized at low temps. by hydrothermal treatment of LiOH·H2O aq. solns. contg. powd. HxMO2 phases. The reaction mechanism and the influence of temp., pressure, H2O diln. and precursor ratio on the ion exchange process, were studied. Single-phase LiMO2 can be obtained in 48 h at 160° at an air pressure of 60 bars from a MOOH/LiOH·H2O/H2O mixt. The progress of the exchange reaction for M = Co was monitored in situ using an autoclave which allowed sampling during the reaction. According to TEM and XRD studies the reaction occurs by surface H+-Li+ exchange and is accompanied by a progressive breaking of the particles due interfacial collapse. IR studies indicate that the LiCoO2 and LiNiO2 phases obtained are contaminated by carbonates that can be removed from LiCoO2 by washing with water followed by heating in vacuo at 200° for 2 days. When the ion-exchange parameters are controlled, the LiMO2 products exhibit an electrochem. performance comparable to that of high-temp. produced phases.
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    25. 25
      Mishra, K.; Pundir, S. S.; Rai, D. K. All-solid-state Proton Battery Using Gel Polymer Electrolyte. AIP Conf. Proc. 2014, 1591, 633,  DOI: 10.1063/1.4872700
      25
      All-solid-state proton battery using gel polymer electrolyte
      Mishra, Kuldeep; Pundir, S. S.; Rai, D. K.
      AIP Conference Proceedings (2014), 1591 (1, Solid State Physics), 633-635CODEN: APCPCS; ISSN:0094-243X. (American Institute of Physics)
      A proton conducting gel polymer electrolyte system; PMMA+NH4SCN+EC/PC, has been prepd. The highest ionic cond. obtained from the system is 2.5 × 10-4 S cm-1. The optimized compn. of the gel electrolyte has been used to fabricate a proton battery with Zn/ZnSO4·7H2O anode and MnO2 cathode. The open circuit voltage of the battery is 1.4 V and the highest energy d. is 5.7 W h kg-1 for low current drain. (c) 2014 American Institute of Physics.
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    26. 26
      Smith, J. P.; Brown, W. E.; Lehr, J. R. Structure of Crystalline Phosphoric Acid. J. Am. Chem. Soc. 1955, 77, 2728– 2730,  DOI: 10.1021/ja01615a013
      26
      Structure of crystalline phosphoric acid
      Smith, James P.; Brown, Walter E.; Lehr, James R.
      Journal of the American Chemical Society (1955), 77 (), 2728-30CODEN: JACSAT; ISSN:0002-7863.
      The crystal structure of anhyd. orthophosphoric acid was detd. by means of 2-dimension Fourier projections. The unit-cell dimensions are a = 5.80 ± 0.02, b = 4.85 ± 0.02, c = 11.62 ± 0.04 A., and angle β = 95°20' ± 20'. The space group is C52h-P21/c with 4 formula wts. of H3PO4 per unit cell. The lattice consts. of orthophosphoric acid hemihydrate are a = 7.94 ± 0.04, b = 12.94 ± 0.02, c = 7.38 ± 0.02 A., and angle β = 109°25' ± 30'. The space group is C52h-P21/a with 4 formula wts. of 2H3PO4.H2O per unit cell. The optical and morphological properties of the 2 cryst. forms of the acid are given.
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    27. 27
      Dippel, T.; Kreuer, K.; Lassegues, J.; Rodriguez, D. Proton Conductivity in Fused Phosphoric Acid; A 1H/31P PFG-NMR and QNS Study. Solid State Ionics 1993, 61, 41– 46,  DOI: 10.1016/0167-2738(93)90332-W
      27
      Proton conductivity in fused phosphoric acid; A 1H/31P PFG-NMR and QNS study
      Dippel, Th.; Kreuer, K. D.; Lassegues, J. C.; Rodriguez, D.
      Solid State Ionics (1993), 61 (1-3), 41-6CODEN: SSIOD3; ISSN:0167-2738.
      The self-diffusion coeffs. D(1H) and D(31P) for fused H3PO4 were measured by PFG (pulsed field gradient) NMR. The results are discussed together with cond., self-dissocn., and QNS (quasielastic neutron scattering) data. Conduction in H3PO4 appears to be predominately protonic (tH+ ≈ 0.975), and structure diffusion is proposed as the operating fast conduction and diffusion mechanism. There is an indication for correlated proton transfer.
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    28. 28
      Swift, M. W.; Qi, Y. First-principles Prediction of Potentials and Space-charge Layers in All-solid-state Batteries. Phys. Rev. Lett. 2019, 122, 167701  DOI: 10.1103/PhysRevLett.122.167701
      28
      First-Principles Prediction of Potentials and Space-Charge Layers in All-Solid-State Batteries
      Swift, Michael W.; Qi, Yue
      Physical Review Letters (2019), 122 (16), 167701pp.CODEN: PRLTAO; ISSN:1079-7114. (American Physical Society)
      As all-solid-state batteries (SSBs) develop as an alternative to traditional cells, a thorough theor. understanding of driving forces behind battery operation is needed. We present a fully first-principles-informed model of potential profiles in SSBs and apply the model to the Li/LiPON/LixCoO2 system. The model predicts interfacial potential drops driven by both electron transfer and Li+ space-charge layers that vary with the SSB's state of charge. The results suggest a lower electronic ionization potential in the solid electrolyte favors Li+ transport, leading to higher discharge power.
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    29. 29
      Neugebauer, J.; Van de Walle, C. G. Hydrogen in GaN: Novel Aspects of a Common Impurity. Phys. Rev. Lett. 1995, 75, 4452– 4455,  DOI: 10.1103/PhysRevLett.75.4452
      29
      Hydrogen in GaN: novel aspects of a common impurity
      Neugebauer, Jorg; Van de Walle, Chris G.
      Physical Review Letters (1995), 75 (24), 4452-5CODEN: PRLTAO; ISSN:0031-9007. (American Physical Society)
      The authors have studied electronic structure, energetics, and migration of H and H complexes in GaN, based on 1st-principles total-energy calcns. The calcns. reveal a no. of features very different from those exhibited by H in more traditional semiconductors such as Si or GaAs: a very large neg.-U effect (U ≈ 2.4 eV), the instability of the bond-center site, high energies for H mols., and an unusual geometry for the Mg-H complex. All of these features are a consequence of distinctive properties of GaN, namely, the strongly ionic nature and the large bond strength of the Ga-N bond. The authors propose a simple model for the neg.-U behavior, which should valid for H in any semiconductor.
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    30. 30
      Fingerle, M.; Buchheit, R.; Sicolo, S.; Albe, K.; Hausbrand, R. Reaction and Space Charge Layer Formation at the LiCoO2–LiPON Interface: Insights on Defect Formation and Ion Energy Level Alignment by a Combined Surface Science–Simulation Approach. Chem. Mater. 2017, 29, 7675– 7685,  DOI: 10.1021/acs.chemmater.7b00890
      30
      Reaction and Space Charge Layer Formation at the LiCoO2-LiPON Interface: Insights on Defect Formation and Ion Energy Level Alignment by a Combined Surface Science-Simulation Approach
      Fingerle, Mathias; Buchheit, Roman; Sicolo, Sabrina; Albe, Karsten; Hausbrand, Rene
      Chemistry of Materials (2017), 29 (18), 7675-7685CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
      In this contribution, we investigate the formation and evolution of LiCoO2-LiPON interfaces upon annealing using photoelectron spectroscopy. We identify interlayer compds. related to the deposition process and study the chem. reactions leading to interlayer formation. Based on the structure of the pristine interface as well as on its evolution upon annealing, we relate reaction layer and space charge layer formation to chem. potential differences between the two materials. The results are discussed in terms of a combined Li-ion and electron interface energy level scheme providing insights into fundamental charge transfer processes. In constructing the energy level alignment, we take into account calcd. defect formation energies of lithium in the cathode and solid electrolyte.
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    31. 31
      Tukamoto, H.; West, A. R. Electronic Conductivity of LiCoO2 and Its Enhancement by Magnesium Doping. J. Electrochem. Soc. 1997, 144, 3164– 3168,  DOI: 10.1149/1.1837976
      31
      Electronic conductivity of LiCoO2 and its enhancement by magnesium doping
      Tukamoto, H.; West, A. R.
      Journal of the Electrochemical Society (1997), 144 (9), 3164-3168CODEN: JESOAN; ISSN:0013-4651. (Electrochemical Society)
      LiCoO2 the active cathode material in com. rechargeable lithium batteries, is shown to be a p-type semiconductor, assocd. with the presence of a small concn. of Co4+ ions. Its cond. at room temp. can be increased by over two order of magnitude, to ∼0.5 S cm-1, by partial substitution of Co3+ by Mg2+ and compensating hole creation. The electrochem. performance of LiMg0.05Co0.95O2 is comparable to that of LiCoO2; a small redn. in capacity, assocd. with a redn. in Co3+ content, occurs but good reversibility is retained and, in contrast to LiCoO2, the Mg-doped material is single phase throughout the charge/discharge cycle.
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    32. 32
      Momma, K.; Izumi, F. VESTA 3 for Three-dimensional Visualization of Crystal, Volumetric and Morphology Data. J. Appl. Crystallogr. 2011, 44, 1272– 1276,  DOI: 10.1107/S0021889811038970
      32
      VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data
      Momma, Koichi; Izumi, Fujio
      Journal of Applied Crystallography (2011), 44 (6), 1272-1276CODEN: JACGAR; ISSN:0021-8898. (International Union of Crystallography)
      VESTA is a 3D visualization system for crystallog. studies and electronic state calcns. It was upgraded to the latest version, VESTA 3, implementing new features including drawing the external morphpol. of crysals; superimposing multiple structural models, volumetric data and crystal faces; calcn. of electron and nuclear densities from structure parameters; calcn. of Patterson functions from the structure parameters or volumetric data; integration of electron and nuclear densities by Voronoi tessellation; visualization of isosurfaces with multiple levels, detn. of the best plane for selected atoms; an extended bond-search algorithm to enable more sophisticated searches in complex mols. and cage-like structures; undo and redo is graphical user interface operations; and significant performance improvements in rendering isosurfaces and calcg. slices.
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    33. 33
      Johnson, III, R. D. NIST101. Computational Chemistry Comparison and Benchmark Database, https://cccbdb.nist.gov/.
      There is no corresponding record for this reference.
    34. 34
      Van de Walle, C. G.; Neugebauer, J. Universal Alignment of Hydrogen Levels in Semiconductors, Insulators and Solutions. Nature 2003, 423, 626– 628,  DOI: 10.1038/nature01665
      34
      Universal alignment of hydrogen levels in semiconductors, insulators and solutions
      Van de Walle, Chris G.; Neugebauer, J.
      Nature (London, United Kingdom) (2003), 423 (6940), 626-628CODEN: NATUAS; ISSN:0028-0836. (Nature Publishing Group)
      Hydrogen strongly affects the electronic and structural properties of many materials. It can bind to defects or to other impurities, often eliminating their elec. activity: this effect of defect passivation is crucial to the performance of many photovoltaic and electronic devices. A fuller understanding of hydrogen in solids is required to support development of improved hydrogen-storage systems, proton-exchange membranes for fuel cells, and high-permittivity dielecs. for integrated circuits. In chem. and in biol. systems, there also were many efforts to correlate proton affinity and deprotonation with host properties. Here the authors report a systematic theor. study (based on ab initio methods) of hydrogen in a wide range of hosts, which reveals the existence of a universal alignment for the electronic transition level of hydrogen in semiconductors, insulators and even aq. solns. This alignment allows the prediction of the elec. activity of hydrogen in any host material once some basic information about the band structure of that host is known. The authors present a phys. explanation that connects the behavior of hydrogen to the line-up of electronic band structures at heterojunctions.
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    35. 35
      Xu, G.; Li, J.; Wang, C.; du, X.; Lu, D.; Xie, B.; Wang, X.; Lu, C.; Liu, H.; Dong, S.; Cui, G.; Chen, L. The Formation/Decomposition Equilibrium of LiH and Its Contribution on Anode Failure in Practical Lithium Metal Batteries. Angew. Chem., Int. Ed. 2021, 60, 7770– 7776,  DOI: 10.1002/anie.202013812
      35
      The Formation/Decomposition Equilibrium of LiH and its Contribution on Anode Failure in Practical Lithium Metal Batteries
      Xu, Gaojie; Li, Jiedong; Wang, Chao; Du, Xiaofan; Lu, Di; Xie, Bin; Wang, Xiao; Lu, Chenglong; Liu, Haisheng; Dong, Shanmu; Cui, Guanglei; Chen, Liquan
      Angewandte Chemie, International Edition (2021), 60 (14), 7770-7776CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
      Discovering the underlying reason for Li anode failure is a crit. step towards applications of lithium metal batteries (LMBs). In this work, we conduct deuterium-oxide (D2O) titrn. expts. in a novel online gas anal. mass spectrometry (MS) system, to det. the content of metallic Li and lithium hydride (LiH) in cycled Li anodes disassembled from practical LiCoO2/Li LMBs. The practical cell is comprised of ultrathin Li anode (50 μm), high loading LiCoO2 (17 mg cm-2, 2.805 mAh cm-2) and different formulated electrolytes. Our results suggest that the amt. of LiH accumulation is neg. correlated with cyclability of practical LMBs. More importantly, we reveal a temp. sensitive equil. (Li + 1/2 H2 .dblharw. LiH) governing formation and decompn. process of LiH at Li anode. We believe that the unusual understanding provided by this study will draw forth more insightful efforts to realize efficient Li protection and the ultimate applications of "holy grail" LMBs.
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    36. 36
      Wakabayashi, Y.; Shirasawa, T.; Voegeli, W.; Takahashi, T. Observation of Structure of Surfaces and Interfaces by Synchrotron X-ray Diffraction: Atomic-scale Imaging and Time-resolved Measurements. J. Phys. Soc. Jpn. 2018, 87, 061010  DOI: 10.7566/JPSJ.87.061010
      There is no corresponding record for this reference.
    37. 37
      Zheng, S. J.; Fisher, C. A. J.; Hitosugi, T.; Kumatani, A.; Shiraki, S.; Ikuhara, Y. H.; Kuwabara, A.; Moriwake, H.; Oki, H.; Ikuhara, Y. Antiphase Inversion Domains in Lithium Cobaltite Thin Films Deposited on Single-crystal Sapphire Substrates. Acta Mater. 2013, 61, 7671– 7678,  DOI: 10.1016/j.actamat.2013.09.004
      37
      Antiphase inversion domains in lithium cobaltite thin films deposited on single-crystal sapphire substrates
      Zheng, S. J.; Fisher, C. A. J.; Hitosugi, T.; Kumatani, A.; Shiraki, S.; Ikuhara, Y. H.; Kuwabara, A.; Moriwake, H.; Oki, H.; Ikuhara, Y.
      Acta Materialia (2013), 61 (20), 7671-7678CODEN: ACMAFD; ISSN:1359-6454. (Elsevier Ltd.)
      Antiphase inversion domains in LiCoO2 thin films prepd. by pulsed laser deposition on sapphire single-crystal substrates are analyzed using a combination of (scanning) TEM and first-principles calcns. Domains form epitaxially on the substrates with orientation relationships of [1 1 ‾2 0]LiCoO2(0001)LiCoO2//[1 ‾1 0 0]α-Al2O3(0 0 0 1)α-Al2O3 and [1 ‾1 2 0]LiCoO2(0 0 0 1)LiCoO2//[1 ‾1 0 0]α-Al2O3(0 0 0 1)α-Al2O3. In addn., substrate/film interfaces with the above orientation relationships always have the same stacking sequence of Al-O-Co-O-Li-O. This is confirmed to be the most energetically stable stacking arrangement according to first-principles calcns. Individual domains form as a result of steps one (0 0 0 1) O-Al-O spacing in height on the otherwise flat substrate surface. Because the orientation of adjacent (0 0 0 1) AlO6 octahedra in Al2O3 are rotated by 180°, while LiO6 and CoO6 octahedra in LiCoO2 are all aligned in the same direction, substrate steps produce LiCoO2 domains rotated 180° relative to their neighbors. The similar size of oxygen octahedra in the two materials also means that the step height is close to the layer spacing in LiCoO2, so that (0 0 0 1) Li and Co layers of adjacent domains are shifted by one layer relative to each other at each domain boundary, aligning Li layers with Co layers across the boundary. The combination of these two effects generates antiphase inversion domains. The domain boundaries effectively sever Li-ion diffusion pathways in the (0 0 0 1) planes between domains and thus are expected to have a detrimental effect on Li-ion cond.
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    38. 38
      Blöchl, P. E. Projector Augmented-wave Method. Phys. Rev. B 1994, 50, 17953– 17979,  DOI: 10.1103/PhysRevB.50.17953
      38
      Projector augmented-wave method
      Blochl
      Physical review. B, Condensed matter (1994), 50 (24), 17953-17979 ISSN:0163-1829.
      There is no expanded citation for this reference.
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    39. 39
      Perdew, J. P.; Burke, K.; Ernzerhof, M. Generalized Gradient Approximation Made Simple. Phys. Rev. Lett. 1996, 77, 3865,  DOI: 10.1103/PhysRevLett.77.3865
      39
      Generalized gradient approximation made simple
      Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
      Physical Review Letters (1996), 77 (18), 3865-3868CODEN: PRLTAO; ISSN:0031-9007. (American Physical Society)
      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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    40. 40
      Klimeš, J.; Bowler, D. R.; Michaelides, A. Chemical Accuracy for the van der Waals Density Functional. J. Phys. Condens. Matter. 2010, 22, 022201  DOI: 10.1088/0953-8984/22/2/022201
      42
      Chemical accuracy for the van der Waals density functional
      Klimes, Jiri; Bowler, David R.; Michaelides, Angelos
      Journal of Physics: Condensed Matter (2010), 22 (2), 022201/1-022201/5CODEN: JCOMEL; ISSN:0953-8984. (Institute of Physics Publishing)
      The non-local van der Waals d. functional (vdW-DF) of Dion et al is a very promising scheme for the efficient treatment of dispersion bonded systems. We show here that the accuracy of vdW-DF can be dramatically improved both for dispersion and hydrogen bonded complexes through the judicious selection of its underlying exchange functional. New and published exchange functionals are identified that deliver much better than chem. accuracy from vdW-DF for the S22 benchmark set of weakly interacting dimers and for water clusters. Improved performance for the adsorption of water on salt is also obtained.
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    41. 41
      Klimeš, J.; Bowler, D. R.; Van der Michaelides, A. Waals Density Functionals Applied to Solids. Phys. Rev. B 2011, 83, 195131  DOI: 10.1103/PhysRevB.83.195131
      43
      Van der Waals density functionals applied to solids
      Klimes, Jiri; Bowler, David R.; Michaelides, Angelos
      Physical Review B: Condensed Matter and Materials Physics (2011), 83 (19), 195131/1-195131/13CODEN: PRBMDO; ISSN:1098-0121. (American Physical Society)
      The van der Waals d. functional (vdW-DF) of M. Dion et al. [Phys. Rev. Lett. 92, 246401 (2004)] is a promising approach for including dispersion in approx. d. functional theory exchange-correlation functionals. Indeed, an improved description of systems held by dispersion forces has been demonstrated in the literature. However, despite many applications, std. general tests on a broad range of materials including traditional "hard" matter such as metals, ionic compds., and insulators are lacking. Such tests are important not least because many of the applications of the vdW-DF method focus on the adsorption of atoms and mols. on the surfaces of solids. Here we calc. the lattice consts., bulk moduli, and atomization energies for a range of solids using the original vdW-DF and several of its offspring. We find that the original vdW-DF overestimates lattice consts. in a similar manner to how it overestimates binding distances for gas-phase dimers. However, some of the modified vdW functionals lead to av. errors which are similar to those of PBE or better. Likewise, atomization energies that are slightly better than from PBE are obtained from the modified vdW-DFs. Although the tests reported here are for hard solids, not normally materials for which dispersion forces are thought to be important, we find a systematic improvement in cohesive properties for the alkali metals and alkali halides when nonlocal correlations are accounted for.
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    42. 42
      Kresse, G.; Furthmüller, J. Efficient Iterative Schemes for Ab Initio Total-energy Calculations Using a Plane-wave Basis Set. Phys. Rev. B 1996, 54, 11169– 11186,  DOI: 10.1103/PhysRevB.54.11169
      40
      Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
      Kresse, G.; Furthmueller, J.
      Physical Review B: Condensed Matter (1996), 54 (16), 11169-11186CODEN: PRBMDO; ISSN:0163-1829. (American Physical Society)
      The authors present an efficient scheme for calcg. the Kohn-Sham ground state of metallic systems using pseudopotentials and a plane-wave basis set. In the first part the application of Pulay's DIIS method (direct inversion in the iterative subspace) to the iterative diagonalization of large matrixes will be discussed. This approach is stable, reliable, and minimizes the no. of order Natoms3 operations. In the second part, we will discuss an efficient mixing scheme also based on Pulay's scheme. A special "metric" and a special "preconditioning" optimized for a plane-wave basis set will be introduced. Scaling of the method will be discussed in detail for non-self-consistent and self-consistent calcns. It will be shown that the no. of iterations required to obtain a specific precision is almost independent of the system size. Altogether an order Natoms2 scaling is found for systems contg. up to 1000 electrons. If we take into account that the no. of k points can be decreased linearly with the system size, the overall scaling can approach Natoms. They have implemented these algorithms within a powerful package called VASP (Vienna ab initio simulation package). The program and the techniques have been used successfully for a large no. of different systems (liq. and amorphous semiconductors, liq. simple and transition metals, metallic and semiconducting surfaces, phonons in simple metals, transition metals, and semiconductors) and turned out to be very reliable.
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    43. 43
      Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y.; Humphreys, C. J.; Sutton, A. P. Electron-energy-loss Spectra and the Structural Stability of Nickel Oxide: An LSDA+ U Study. Phys. Rev. B 1998, 57, 1505– 1509,  DOI: 10.1103/PhysRevB.57.1505
      41
      Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study
      Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y.; Humphreys, C. J.; Sutton, A. P.
      Physical Review B: Condensed Matter and Materials Physics (1998), 57 (3), 1505-1509CODEN: PRBMDO; ISSN:0163-1829. (American Physical Society)
      By taking better account of electron correlations in the 3d shell of metal ions in Ni oxide it is possible to improve the description of both electron energy loss spectra and parameters characterizing the structural stability of the material compared with local spin d. functional theory.
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    44. 44
      Freysoldt, C.; Neugebauer, J.; Van de Walle, C. G. Fully Ab Initio Finite-size Corrections for Charged-defect Supercell Calculations. Phys. Rev. Lett. 2009, 102, 016402  DOI: 10.1103/PhysRevLett.102.016402
      44
      Fully Ab Initio Finite-Size Corrections for Charged-Defect Supercell Calculations
      Freysoldt, Christoph; Neugebauer, Jorg; Van de Walle, Chris G.
      Physical Review Letters (2009), 102 (1), 016402/1-016402/4CODEN: PRLTAO; ISSN:0031-9007. (American Physical Society)
      In ab initio theory, defects are routinely modeled by supercells with periodic boundary conditions. Unfortunately, the supercell approxn. introduces artificial interactions between charged defects. Despite numerous attempts, a general scheme to correct for these is not yet available. We propose a new and computationally efficient method that overcomes limitations of previous schemes and is based on a rigorous anal. of electrostatics in dielec. media. Its reliability and rapid convergence with respect to cell size is demonstrated for charged vacancies in diamond and GaAs.
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    45. 45
      Imamoğlu, A. Cavity QED Based on Collective Magnetic Dipole Coupling: Spin Ensembles as Hybrid Two-level Systems. Phys. Rev. Lett. 2009, 102, 083602  DOI: 10.1103/PhysRevLett.102.083602
      45
      Cavity QED Based on Collective Magnetic Dipole Coupling: Spin Ensembles as Hybrid Two-Level Systems
      Imamoglu, Atac
      Physical Review Letters (2009), 102 (8), 083602/1-083602/4CODEN: PRLTAO; ISSN:0031-9007. (American Physical Society)
      The authors analyze the magnetic dipole coupling of an ensemble of spins to a superconducting microwave stripline structure, incorporating a Josephson junction based transmon qubit. This system is described by an embedded Jaynes-Cummings model: in the strong coupling regime, collective spin-wave excitations of the ensemble of spins pick up the nonlinearity of the cavity mode, such that the 2 lowest eigenstates of the coupled spin wave-microwave cavity-Josephson junction system define a hybrid 2-level system. The proposal described here enables new avenues for nonlinear optics using optical photons coupled to spin ensembles via Raman transitions. The possibility of strong coupling cavity QED with magnetic dipole transitions also opens up the possibility of extending quantum information processing protocols to spins in Si or graphene, without the need for single-spin confinement.
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    46. 46
      Reuter, K.; Scheffler, M. Composition, Structure, and Stability of RuO2 (110) as a Function of Oxygen Pressure. Phys. Rev. B 2001, 65, 035406  DOI: 10.1103/PhysRevB.65.035406
      There is no corresponding record for this reference.
    47. 47
      Koettgen, J.; Zacherle, T.; Grieshammer, S.; Martin, M. Ab Initio Calculation of the Attempt Frequency of Oxygen Diffusion in Pure and Samarium Doped Ceria. Phys. Chem. Chem. Phys. 2017, 19, 9957– 9973,  DOI: 10.1039/c6cp04802a
      47
      Ab initio calculation of the attempt frequency of oxygen diffusion in pure and samarium doped ceria
      Koettgen, Julius; Zacherle, Tobias; Grieshammer, Steffen; Martin, Manfred
      Physical Chemistry Chemical Physics (2017), 19 (15), 9957-9973CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)
      The rate of oxygen ion jumps in a solid oxide depends not only on the activation energy but also on the pre-exponential factor of diffusion. In order to allow a fully ab initio prediction of the oxygen ion cond. in pure and samarium doped ceria, we calcd. the attempt frequency for an oxygen ion jump from first principles combining DFT + U, the NEB method, phonon calcns. and the transition state theory. Different definitions of the jump attempt frequency are presented. The equivalence of the Eyring and the Vineyard method is shown without restriction to the Gamma point. Convergence checks of the phonon mesh reveal that the common redn. to the Gamma point is not sufficient to calc. the attempt frequency. Calcns. of Sm doped ceria revealed an increase of the prefactor. The attempt frequency for the const. pressure case in quasi-harmonic approxn. is larger than the attempt frequency at const. vol. in harmonic approxn. The calcd. electronic energies, enthalpies and entropies of migration are in agreement with the exptl. diffusion coeffs. and activation energies.
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    48. 48
      Kyrtsos, A.; Matsubara, M.; Bellotti, E. Migration Mechanisms and Diffusion Barriers of Carbon and Native Point Defects in GaN. Phys. Rev. B 2016, 93, 245201  DOI: 10.1103/PhysRevB.93.245201
      48
      Migration mechanisms and diffusion barriers of carbon and native point defects in GaN
      Kyrtsos, Alexandros; Matsubara, Masahiko; Bellotti, Enrico
      Physical Review B (2016), 93 (24), 245201/1-245201/10CODEN: PRBHB7; ISSN:2469-9950. (American Physical Society)
      A review. Carbon related defects are readily incorporated in GaN due to its abundance during growth both with MBE and MOCVD techniques. Employing first-principles calcns., we compute the migration barriers of carbon interstitials and we discuss possible relevant mechanisms of diffusion in the wurtzite GaN crystal. In addn., we calc. the migration barriers for the diffusion of the native defects of the crystal, i.e., gallium and nitrogen interstitials and vacancies. The min. energy path and the migration barriers of these defects are obtained using the nudged elastic band method with the climbing image modification. In addn., the dimer method is used to independently det. the results. The results yield a quant. description of carbon diffusion in GaN allowing for the detn. of the most preferable migration paths.
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  • Supporting Information

    Supporting Information

    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsami.1c17945.

    • Fabrication of gas-exposed thin-film batteries, X-ray crystal truncation rod (CTR) scattering analysis, estimation of the interface resistance using an equivalent circuit, electrochemical properties of the pure gas-exposed batteries, impedance spectra of the H2O-vapor-exposed battery, parameters of the equivalent circuits used for the gas-exposed batteries, capacity retention, annealing recovery of the air-exposed battery, annealing processes and performance of the H2O-vapor-exposed battery, parameters of the equivalent circuits used for the gas-exposed batteries after the annealing process, optimized geometry of a proton occupying a Li vacancy site in the LiCoO2 structure, comparison of different LCO proton interstitial sites, and the time-of-flight secondary ion mass spectroscopy spectrum for H– and Li– species (PDF)


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