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Crystalline LiPON as a Bulk-Type Solid Electrolyte

  • Pedro López-Aranguren
    Pedro López-Aranguren
    Center for Cooperative Research on Alternative Energies (CIC energiGUNE), Basque Research and Technology Alliance (BRTA), Parque Tecnológico de Álava, Albert Einstein, 48, 01510 Vitoria-Gasteiz, Spain
  • Marine Reynaud*
    Marine Reynaud
    Center for Cooperative Research on Alternative Energies (CIC energiGUNE), Basque Research and Technology Alliance (BRTA), Parque Tecnológico de Álava, Albert Einstein, 48, 01510 Vitoria-Gasteiz, Spain
    *E-mail: [email protected]
  • Paweł Głuchowski
    Paweł Głuchowski
    Institute of Low Temperature and Structure Research, Polish Academy of Sciences, Okólna 2, 50-422 Wrocław, Poland
  • Ainhoa Bustinza
    Ainhoa Bustinza
    Center for Cooperative Research on Alternative Energies (CIC energiGUNE), Basque Research and Technology Alliance (BRTA), Parque Tecnológico de Álava, Albert Einstein, 48, 01510 Vitoria-Gasteiz, Spain
  • Montserrat Galceran
    Montserrat Galceran
    Center for Cooperative Research on Alternative Energies (CIC energiGUNE), Basque Research and Technology Alliance (BRTA), Parque Tecnológico de Álava, Albert Einstein, 48, 01510 Vitoria-Gasteiz, Spain
  • Juan Miguel López del Amo
    Juan Miguel López del Amo
    Center for Cooperative Research on Alternative Energies (CIC energiGUNE), Basque Research and Technology Alliance (BRTA), Parque Tecnológico de Álava, Albert Einstein, 48, 01510 Vitoria-Gasteiz, Spain
  • Michel Armand
    Michel Armand
    Center for Cooperative Research on Alternative Energies (CIC energiGUNE), Basque Research and Technology Alliance (BRTA), Parque Tecnológico de Álava, Albert Einstein, 48, 01510 Vitoria-Gasteiz, Spain
  • , and 
  • Montse Casas-Cabanas
    Montse Casas-Cabanas
    Center for Cooperative Research on Alternative Energies (CIC energiGUNE), Basque Research and Technology Alliance (BRTA), Parque Tecnológico de Álava, Albert Einstein, 48, 01510 Vitoria-Gasteiz, Spain
    IKERBASQUE, Basque Foundation for Science, María Díaz de Haro 3, 48013 Bilbao, Spain
Cite this: ACS Energy Lett. 2021, 6, 2, 445–450
Publication Date (Web):January 12, 2021
https://doi.org/10.1021/acsenergylett.0c02336

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Abstract

In this work, a new bulk Li3.6PO3.4N0.6 crystalline polymorph has been prepared from low-cost precursors, following a simple ball-milling procedure. The densified powder exhibits a conductivity of 5.0 × 10–6 S cm–1 at 70 °C and an electrochemical stability allowing operation with high-voltage materials up to 5.0 V vs Li/Li+. Stripping and plating of lithium in a symmetric cell demonstrates the forthcoming bulk application of LiPON in electrochemical devices. Widening the use of lithium phosphorus oxynitride compositions to bulk solid-state batteries will have relevant implications because of its unique compatibility with both high-voltage electroactive materials and lithium metal and its low density.

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Lithium phosphorus oxynitride (LiPON) compositions first received significant attention in the 1990s as solid electrolyte (SEs) for the development of thin-film solid-state batteries (SSBs). (1,2) LiPONs are commonly prepared via sputtering of Li3PO4 in a N2 atmosphere, resulting in amorphous glass thin films with a wide range of compositions LixPOyNz (2.6 ≤ x ≤ 3.5, 1.9 ≤ y ≤ 3.8, 0.1 ≤ z ≤ 1.3). (3−5) Unlike other SEs, sputtered s-LiPON (where the s denotes “sputtered”) possesses desirable characteristics. (6) First, LiPONs are less sensitive to air than other solid electrolytes, such as Li7La3Zr2O12 (LLZO) garnet or sulfides. Second, in contrast to Li1+xAlxTi2–x(PO4)3 (LATP) or sulfide-based electrolytes, which are easily reduced in contact with Li and form unfavorable solid electrolyte interfaces (SEI), (8−10) a stable and favorable SEI is formed between Li metal and LiPON as revealed by recent studies. (11) In addition, LiPON is one of the few stable solid-electrolyte materials that has enabled the fabrication of anodeless batteries. (12,13) Indeed, excellent electrochemical results have been reported in thin-film batteries using s-LiPONs as the SE, in combination with positive active materials such as TiS2, LiMn2O4, and LiCoO2. (14,15) However, these devices do not exceed ca. 1 cm2 with thicknesses of 10 μm, (14,15) because of its limited ionic conductivity (∼2 × 10–6 S cm–1 at room temperature), (6) and they operate at low current densities (on the order of tens of μA cm–2). Moreover, the limitations of the sputtering technique hamper upscaling toward cells delivering capacities of hundreds of milliampere-hours or larger. Therefore, the synthesis of a stable bulk b-LiPON (where b denotes “bulk”) remains critical for the transition toward its application in SSBs.

Ceramic SEs are one of the most promising approaches to build safe, high-powered, and high-energy density batteries, although this premise relies on the use of a Li-metal anode (7,10) paired with high-voltage cathode materials such as layered oxides. The specific weight of the SE material has a critical impact on the energy density of the final device. A SE thickness of <50 μm is required to provide competitive volumetric and gravimetric energy densities (Ev, Eg). (16) Indeed, electrolytes including heavy metals (such as LLZO) must compensate for their density (∼4.8 g cm–3) with a thickness of <20 μm (17) in order to attain competitive energy density, which, currently, is technologically challenging. Therefore, the low density of LiPONs (∼2.4 g cm–3) provides considerable motivation for its development as bulk SE material. Figure 1 compares the expected theoretical gravimetric and volumetric energy densities (Eg and Ev, respectively) of high-voltage Li-metal SSBs, including either a b-LiPON, a ceramic LLZO, or a glass-ceramic LATP as SEs. The cell models consider a thickness of 50 μm. The cathode composition includes 75 wt % of NMC622 active material, 5 wt % of carbon C65, and 20 wt % of SE. Table S1 in the Supporting Information summarizes all the parameters taken into account for the calculations. Ev ranges from 200 Wh l–1 to ca. 1000 Wh l–1 for cathode loading between 1 and 5 mAh cm–2, without relevant differences between the electrolytes. However, pronounced differences are observed for the trend of Eg: in the best scenario, with a cathode loading of 5 mAh cm–2, LiPON and LATP light electrolytes lead to Eg values as high as 320 Wh kg–1 (i.e., 60% higher than for the heavier LLZO). Indeed, according to our calculations, the thickness of the LLZO electrolyte should be reduced down to the challenging value of 30 μm in order to reach similar Eg values. Such low thicknesses, as well as the high sintering temperature, seriously challenge the processing at a large scale. (18,19)

Figure 1

Figure 1. (a) Expected theoretical gravimetric and volumetric energy densities (Eg and Ev, respectively) of high-voltage Li-metal SSBs, as a function of the cathode loading and including LiPON, LATP, or LLZO as SEs. (b) Schematic representation of the cell model considered for the theoretical predictions shown in panel (a).

To the best of our knowledge, only a couple of crystalline forms of LiPON have been reported so far: Li0.88PO3.73N0.14 (20) and Li2PO2N; (21) both of them with limited ionic conductivity at room temperature (∼1 × 10–13 S cm–1). While these two phases were obtained from solid-state reactions under a controlled atmosphere at high temperatures (600 and 950 °C, respectively), in this work, crystalline b-LiPON was prepared through simple mechanical milling of the low-cost precursors LiPO3 and Li3N for 20 min under Ar (see the Supporting Information for further details). SEM images of the as-synthesized b-LiPON (Figures S1a and S1b in the Supporting Information) revealed particles with irregularly shaped morphology and sizes ranging from 0.1 μm to 1 μm, and with some forming agglomerates.

The powder X-ray diffraction (XRD) pattern of b-LiPON could be indexed in a monoclinic lattice, with the space group P21/m and cell parameters a = 5.098(3) Å, b = 6.158(4) Å, c = 5.324(4) Å, and β = 90.60(4)°. The structure of the new b-LiPON phase was first determined from neutron powder diffraction (NPD) data, using Li3.75Si0.75P0.25O4 (22) as the starting structural model, before being confirmed with a combined refinement of both NPD and XRD patterns (see the Supporting Information for further details on the structure determination). The results of these refinements are presented in Figures 2a and 2b, and in Table 1. The b-LiPON structure is built on a slightly distorted hexagonal close packing (hcp) array of O and N anions. The N anions were found to partially occupy two of the three crystallographically independent oxygen sites O1/N1 and O2/N2. P cations occupy PO3.57(13)N0.43(13) coordination tetrahedra, which are isolated from the others and are alternately pointing in opposite directions (in a regular up–down pattern; see Figure 2c). Li cations were found in six distinct positions, with the same coordination environments as in the Li4SiO4 parent structure: Li6 is found in an octahedral coordination, Li5 is 5-fold coordinated, while the other four Li occupy tetrahedral sites. The individual occupancies of the six Li sites sum 3.67(13), and the overall refined composition is in agreement with the chemical composition Li3.6(1)PO3.4(1)N0.6(1) reproducibly determined on several samples from complementary energy-dispersive X-ray (EDX) spectroscopy, inductively coupled plasma optical emission spectrometry (ICP-OES), and elemental analysis (EA) (see Table S3 in the Supporting Information).

Figure 2

Figure 2. Results of the combined Rietveld refinement of (a) the XRD pattern and (b) the NPD pattern of b-Li3.6PO3.4N0.6. (c) Representation of the refined structure. The six Li positions are shown as purple and white balls, indicating the partial occupation of each site. Positions of P, O, and N are shown as green, orange, and blue balls, respectively, forming tetrahedral cationic sites drawn in green pointing in opposite directions (up–down pattern). (d) 7Li and 31P solid-state MAS NMR spectra of b- Li3.6PO3.4N0.6. One average signal is observed for the Li, while three distinct environments are clearly observed for the P. The attribution and quantification of these three fitted peaks are indicated.

Table 1. Crystal Structure Data of b-Li3.6PO3.4N0.6, Obtained from the Combined Rietveld Refinement of the XRD and NPD Patterns
space group: P21/m ρ = 2.38 g cm–3χ2 = 13.4
    
XRD pattern V = 167.13(19) Å3RBragg = 13.5%
a = 5.098(4) Åb = 6.158(4) Åc = 5.324(4) Åβ = 90.60(4) Å3
    
NPD pattern V = 166.68(7) Å3RBragg = 5.1%
a = 5.094(2) Åb = 6.150(2) Åc = 5.321(2) Åβ = 90.53(2) Å3
atomWyckoff sitex/ay/bz/coccupancy
P12e0.334(3)3/40.677(4)1.0
O1/N14f0.220(2)0.538(2)0.809(3)0.84(5)/0.16(5)
O2/N22e0.363(3)1/40.310(4)0.89(3)/0.11(3)
O32e0.230(4)3/40.396(3)1.0
Li14f0.173(9)0.505(10)0.183(13)0.62(5)
Li22e0.36(2)1/40.66(3)0.46(4)
Li32e0.173(19)1/40.637(18)0.54(4)
Li44f0.362(16)0.531(15)0.16(2)0.38(5)
Li54f0.06(4)0.07(3)1/20.19(4)
Li62e01/400.29(5)

The thermal stability of the b-Li3.6PO3.4N0.6 powder under air was assessed by simultaneous thermogravimetric (TGA), differential thermal (DTA), and mass spectrometry (MS) analyses (see Figure S2a in the Supporting Information). The results evidence an exothermic decomposition reaction with the irreversible loss of N occurring between 450 °C and 650 °C. The weight gain observed in the TGA is in agreement with the oxidation reaction reported elsewhere. (21) The XRD pattern of the powder after heating at 600 °C reveals the decomposition of b-Li3.6PO3.4N0.6 to form Li3PO4 (Figure S2b in the Supporting Information). The XRD of the pellet of b-Li3.6PO3.4N0.6 sintered at 350 °C under air (Figure S2b) confirms the stability the b-Li3.6PO3.4N0.6 phase for the pellets prepared at this temperature for the ionic conductivity measurements presented below. On the other hand, after having observed that b-Li3.6PO3.4N0.6 reacts with water (not shown), we observed that, while b-Li3.6PO3.4N0.6 evolves in a few days to form Li2CO3 when exposed to ambient air, the XRD pattern of the sample remains unchanged under dry atmosphere after 5 days (see Figure S3 in the Supporting Information).

The 7Li solid-state NMR spectrum of b-Li3.6PO3.4N0.6 shows a single resonance with a single exponential longitudinal relaxation time (see Figure 2d, as well as Figure S4b in the Supporting Information). This result suggests that all of the different Li sites are rapidly exchanging positions in the NMR time scale. Three different signals are observed in the 31P NMR spectrum (Figure 2d), which are assigned to the three different environments of phosphorus: PO4 (4.7%), PO3N (56.3%), and PO2N2 (39%). The two-dimensional (2D) 31P–31P-EXSY correlation obtained with a mixing time of 2 s (Figure S4c in the Supporting Information) shows correlation peaks between all different lines, confirming the spatial proximity of all the different phosphorus sites and the single-phase nature of the sample.

Extensive studies show that the insertion of nitrogen into Li3PO4 thin films to obtain compositions such as Li2.88PO3.73N0.14 raises the conductivity from 7 × 10–8 S cm–1 to 2 × 10–6 S cm–1 at room temperature (RT) (1,23−25) and improves the electrochemical stability of the electrolyte up to 5.5 V vs Li/Li+. (1,26,27) The nitridation of lithium phosphate glasses modifies the phosphate anion chains and forms −N═ linked phosphate anion chains. (26) Despite the recent significant progress, how the N is incorporated into the phosphate structure and how it correlates with the ionic conductivity still remains a subject of research. (27) Some studies propose that the increase of the ionic conductivity after the nitridation arises from the increasing structural cross-linking, and decreasing electrostatic energy after replacing the P–O bond by the more covalent P–N one. (26) This bonding has been confirmed in b-Li3.6PO3.4N0.6 by the 31P NMR solid-state spectra shown in Figure 2d.

The ionic conductivity of b-Li3.6PO3.4N0.6 was experimentally measured in order to confirm such enhancement, with respect to the phosphate analogue. Densification of SEs in SSBs is a key step that is required to promote not only high ionic conductivity, but a low-resistive interface with lithium metal, as well as to mitigate the dendrite propagation. The high-pressure and low-temperature (HPLT) sintering technique is particularly suitable for powders exhibiting limited thermal stability, as is the case for our b-Li3.6PO3.4N0.6. (28,29) Pellets ca. 1 mm thick were prepared from the as-synthesized powder quasi-isostatically pressed at 5.5 GPa for 2 min at temperatures ranging from 200 °C to 450 °C, under ambient atmosphere. A b-Li3.6PO3.4N0.6 pellet was also prepared at 1.25 GPa at RT for comparison. The main characteristics of the pellets are summarized in Table S2 in the Supporting Information. The latter compact exhibited a relatively low density of ca. 75% (the theoretical density deduced from the unit-cell volume is 2.38 g cm–3). In contrast, highly dense pellets (87%–95%) were obtained via HPLT sintering, and no clear trend was found for the relative density when increasing the sintering temperature. Indeed, the highest density among the samples explored (95%) was obtained at 250 °C. The morphology of the surface and cross section of the HPLT bodies observed by SEM (Figures S1e and S1f in the Supporting Information) shows a fully and uniformly densified structure. Electrochemical impedance spectroscopy (EIS) measurements were performed on symmetric Li cells of the HPLT pellets (Li|b-Li3.6PO3.4N0.6|Li) (Figure S5a in the Supporting Information). The temperature-dependent conductivity studied from 0 to 80 °C is represented in the Arrhenius plot of Figure 3a. The conductivity of b-Li3.6PO3.4N0.6 pelletized at low pressure and at 25 °C (75% dense) reached 5.6 × 10–8 S cm–1 at 25 °C. This value increased up to 1 order of magnitude for the pellets prepared by HPLT (Figure S5b in the Supporting Information) and reached 6.5 × 10–6 S cm–1 at 70 °C for the pellet pressed at 5.5 GPa and 200 °C (90% dense, Figure 3a). The superior conductivity of HPLT processed pellets is likely due to the higher density attained with this technique, which proves fully suitable for low-temperature densification of ceramics. A similar conductivity was found for samples prepared at lower temperatures (see Table S2), without significant trends associated with the applied sintering temperature (see Figure S5b). Although it still remains insufficient to operate in a full cell at room temperature (∼10–4 S cm–1 required), (30) the progress made in this work with b-Li3.6PO3.4N0.6 is remarkable if compared to s-LiPONs (∼10–6–10–5 S cm–1 at RT and 70 °C), (6) and well above that of γ-Li3PO4 (4.2 × 10–18 S cm–1 at RT) and the other bulk phosphorus oxynitrides reported so far: Li0.88PO3.73N0.14 (1.4 × 10–13 S cm–1 at RT) (31) and Li2PO2N (8.8 × 10–7 S cm–1 at 80 °C). (21)

Figure 3

Figure 3. (a) Ionic conductivity as a function of the temperature for a b-Li3.6PO3.4N0.6 pellet prepared by HPLT at 5.5 GPa and 200 °C. (b) Cyclic voltammetry of b-Li3.6PO3.4N0.6 acquired at 0.5 mV s–1 in the −0.15–5 V vs Li+/Li0 for two cycles. (c) Stripping and plating experiment of a symmetric Li|b-Li3.6PO3.4N0.6|Li cell at 70 °C (inset shows data between 50 h and 70 h).

The average activation energy for b-Li3.6PO3.4N0.6 is 0.55 eV (Table S2), similar to the previously reported crystalline Li2PO2N (0.57 eV) (21) and to that reported for amorphous s-LiPON thin films. The electrical insulating property of b-Li3.6PO3.4N0.6, a sine qua non feature for any electrolyte, was confirmed by chronoamperometry (Figure S6 in the Supporting Information).

Cells prepared with s-LiPONs have been reported to exhibit a wide stability window (0 to 5 V vs Li/Li+). (14,15) Several publications claimed a successful chemical stabilization of the interface between the Li anode and the electrolyte induced by the addition of a thin film of s-LiPON buffer interlayer. (32−34) Indeed, a stable SEI including Li2O, Li3N, and Li3PO4 has been recently unveiled between lithium metal and LiPON. (11) On the cathode side, Put et al. reported that, although s-LiPONs decomposes above 4.5 V vs Li/Li+, the decomposition products (Li4P2O7, LiPO3, and P4O10) are stable at higher potentials and that the layer formed at the interface shields the electrolyte. (35) This explains the excellent cyclability of SSBs using s-LiPON and a high-voltage AM. (36) In this work, the electrochemical stability of the HPLT b-Li3.6PO3.4N0.6 pellets was evaluated by cyclic voltammetry using Li metal disk and silver as reference and working electrodes, respectively. Voltammograms were acquired at 70 °C in the −0.15–5 V range vs Li0/Li+, applying a scan rate of 0.5 mV s–1. The cyclic voltammetry in Figure 3b shows a reductive current below 100 nA cm–2, attributed to the lithium deposition occurring below 0 V. Besides, it demonstrates the excellent electrochemical stability for b-Li3.6PO3.4N0.6 up to 5 V, confirmed by the extremely low oxidative current below 12 nA cm–2 arising from the residual current of the partial electronic conductivity of the solid electrolyte (see Figure S6).

In Li-metal SSBs, the high interface resistance appearing between Li0 and the SE is a major drawback for the battery performance. (37) A symmetric Li|b-Li3.6PO3.4N0.6|Li cell showed a stable ASR of 4 × 105 Ω cm2 at RT after conditioning the cell at 70 °C for 24 h. Interestingly, this resistance has been found to be similar to the Li/LLZO garnet interface, (38) showing a comparable limited effective contact area between the electrolyte and the electrodes. The stripping-plating abilities of b-Li3.6PO3.4N0.6 were examined with the symmetric lithium metal cell at 70 °C (see the Supporting Information for experimental details). The investigation of lithium dendrite nucleation and growth resistance in the cell was performed using prolonged galvanostatic cycling tests (Figure 3c). The SE exhibits an impressive cycling performance with 35 cycles (140 h) without dendrite propagation leading to a short circuit. The current density induced an overpotential of ca. 180 mV in both directions, with a constant voltage indicating a homogeneous dissolution and deposition of metallic Li during the cycling. (39) These results highlight the outstanding progress toward a real bulk full cell including a lithium phosphorus oxynitride composition as SE.

In conclusion, we report the facile synthesis of a bulk crystalline b-Li3.6PO3.4N0.6 solid electrolyte, which may be prepared via mechano-synthesis from the low-cost precursors LiPO3 and Li3N. A high-pressure (5.5 GPa) and low-temperature (200–400 °C) technique is presented here as an interesting approach to obtain pellets 23% denser than the powder pelletized at 1.25 GPa. These highly dense pellets exhibit a conductivity of 3.0 × 10–7 S cm–1 at 25 °C, which increases to 5.0 × 10–6 S cm–1 at 70 °C. The wide electrochemical stability of this electrolyte makes it suitable for use with high-voltage active materials, and the excellent stripping-plating performance of lithium in a symmetric Li|b-Li3.6PO3.4N0.6|Li cell is shown here as a proof of concept that approaches a real electrochemical device. Therefore, this work represents a remarkable step forward for the transition from LiPON thin films toward bulk application in the field of solid-state batteries.

Supporting Information

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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsenergylett.0c02336.

  • Parameters for theoretical calculations, experimental methods, and additional figures (PDF)

  • Crystal structure of b-Li3.6PO3.4N0.6, as determined via NPD (CIF)

  • Crystal structure of b-Li3.6PO3.4N0.6, as determined by XRD (CIF)

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Author Information

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  • Corresponding Author
    • Marine Reynaud - Center for Cooperative Research on Alternative Energies (CIC energiGUNE), Basque Research and Technology Alliance (BRTA), Parque Tecnológico de Álava, Albert Einstein, 48, 01510 Vitoria-Gasteiz, SpainOrcidhttp://orcid.org/0000-0002-0156-8701 Email: [email protected]
  • Authors
    • Pedro López-Aranguren - Center for Cooperative Research on Alternative Energies (CIC energiGUNE), Basque Research and Technology Alliance (BRTA), Parque Tecnológico de Álava, Albert Einstein, 48, 01510 Vitoria-Gasteiz, Spain
    • Paweł Głuchowski - Institute of Low Temperature and Structure Research, Polish Academy of Sciences, Okólna 2, 50-422 Wrocław, PolandOrcidhttp://orcid.org/0000-0003-2566-1422
    • Ainhoa Bustinza - Center for Cooperative Research on Alternative Energies (CIC energiGUNE), Basque Research and Technology Alliance (BRTA), Parque Tecnológico de Álava, Albert Einstein, 48, 01510 Vitoria-Gasteiz, Spain
    • Montserrat Galceran - Center for Cooperative Research on Alternative Energies (CIC energiGUNE), Basque Research and Technology Alliance (BRTA), Parque Tecnológico de Álava, Albert Einstein, 48, 01510 Vitoria-Gasteiz, SpainOrcidhttp://orcid.org/0000-0002-8749-9371
    • Juan Miguel López del Amo - Center for Cooperative Research on Alternative Energies (CIC energiGUNE), Basque Research and Technology Alliance (BRTA), Parque Tecnológico de Álava, Albert Einstein, 48, 01510 Vitoria-Gasteiz, Spain
    • Michel Armand - Center for Cooperative Research on Alternative Energies (CIC energiGUNE), Basque Research and Technology Alliance (BRTA), Parque Tecnológico de Álava, Albert Einstein, 48, 01510 Vitoria-Gasteiz, SpainOrcidhttp://orcid.org/0000-0002-1303-9233
    • Montse Casas-Cabanas - Center for Cooperative Research on Alternative Energies (CIC energiGUNE), Basque Research and Technology Alliance (BRTA), Parque Tecnológico de Álava, Albert Einstein, 48, 01510 Vitoria-Gasteiz, SpainIKERBASQUE, Basque Foundation for Science, María Díaz de Haro 3, 48013 Bilbao, SpainOrcidhttp://orcid.org/0000-0002-9298-2333
  • Notes
    The authors declare no competing financial interest.

Acknowledgments

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The Ministerio de Ciencia, Innovación y Universidades of Spain is greatly acknowledged for the Juan de la Cierva grant, under Reference No. IJCI-2017-32310 and Projects No. ENE2016-81020-R and PID2019-107106RB-C33. We thank N. A. Katcho and J. Carrasco for their contribution with theoretical calculations, and T. Raynaud and A. Pavageau for their assistance with the experiments.

References

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This article references 39 other publications.

  1. 1
    Yu, X.; Bates, J. B.; Jellison, G. E.; Hart, F. X. A Stable Thin-Film Lithium Electrolyte: Lithium Phosphorus Oxynitride. J. Electrochem. Soc. 1997, 144 (2), 524532,  DOI: 10.1149/1.1837443
  2. 2
    Bates, J. B.; Dudney, N. J.; Gruzalski, G. R.; Zuhr, R. A.; Choudhury, A.; Luck, C. F.; Robertson, J. D. Fabrication and Characterization of Amorphous Lithium Electrolyte Thin Films and Rechargeable Thin-Film Batteries. J. Power Sources 1993, 43 (1), 103110,  DOI: 10.1016/0378-7753(93)80106-Y
  3. 3
    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, 647654,  DOI: 10.1016/0167-2738(92)90442-R
  4. 4
    Oudenhoven, J. F. M.; Baggetto, L.; Notten, P. H. L. All-Solid-State Lithium-Ion Microbatteries: A Review of Various Three-Dimensional Concepts. Adv. Energy Mater. 2011, 1 (1), 1033,  DOI: 10.1002/aenm.201000002
  5. 5
    Nowak, S.; Berkemeier, F.; Schmitz, G. Ultra-Thin LiPON Films – Fundamental Properties and Application in Solid State Thin Film Model Batteries. J. Power Sources 2015, 275, 144150,  DOI: 10.1016/j.jpowsour.2014.10.202
  6. 6
    Zheng, F.; Kotobuki, M.; Song, S.; Lai, M. O.; Lu, L. Review on Solid Electrolytes for All-Solid-State Lithium-Ion Batteries. J. Power Sources 2018, 389, 198213,  DOI: 10.1016/j.jpowsour.2018.04.022
  7. 7
    Albertus, P.; Babinec, S.; Litzelman, S.; Newman, A. Status and Challenges in Enabling the Lithium Metal Electrode for High-Energy and Low-Cost Rechargeable Batteries. Nat. Energy 2018, 3 (1), 1621,  DOI: 10.1038/s41560-017-0047-2
  8. 8
    Gao, Z.; Sun, H.; Fu, L.; Ye, F.; Zhang, Y.; Luo, W.; Huang, Y. Promises, Challenges, and Recent Progress of Inorganic Solid-State Electrolytes for All-Solid-State Lithium Batteries. Adv. Mater. 2018, 30, 1870122,  DOI: 10.1002/adma.201870122
  9. 9
    Schnell, J.; Günther, T.; Knoche, T.; Vieider, C.; Köhler, L.; Just, A.; Keller, M.; Passerini, S.; Reinhart, G. All-Solid-State Lithium-Ion and Lithium Metal Batteries – Paving the Way to Large-Scale Production. J. Power Sources 2018, 382, 160175,  DOI: 10.1016/j.jpowsour.2018.02.062
  10. 10
    Janek, J.; Zeier, W. G. A Solid Future for Battery Development. Nature Energy 2016, 1, 1614116144,  DOI: 10.1038/nenergy.2016.141
  11. 11
    Cheng, D.; Wynn, T. A.; Wang, X.; Wang, S.; Zhang, M.; Shimizu, R.; Bai, S.; Nguyen, H.; Fang, C.; Kim, M.; Li, W.; Lu, B.; Kim, S. J.; Meng, Y. S. Unveiling the Stable Nature of the Solid Electrolyte Interphase between Lithium Metal and LiPON via Cryogenic Electron Microscopy. Joule 2020, 4 (11), P2484P2500,  DOI: 10.2139/ssrn.3640837
  12. 12
    Wang, M. J.; Carmona, E.; Gupta, A.; Albertus, P.; Sakamoto, J. Enabling “Lithium-Free” Manufacturing of Pure Lithium Metal Solid-State Batteries through in Situ Plating. Nat. Commun. 2020, 11 (1), 52015209,  DOI: 10.1038/s41467-020-19004-4
  13. 13
    Neudecker, B. J.; Dudney, N. J.; Bates, J. B. Lithium-Free” Thin-Film Battery with In Situ Plated Li Anode. J. Electrochem. Soc. 2000, 147 (2), 517523,  DOI: 10.1149/1.1393226
  14. 14
    Bates, J. B.; Dudney, N. J.; Neudecker, B.; Ueda, A.; Evans, C. D. Thin-Film Lithium and Lithium-Ion Batteries. Solid State Ionics 2000, 135 (1), 3345,  DOI: 10.1016/S0167-2738(00)00327-1
  15. 15
    Patil, A.; Patil, V.; Wook Shin, D.; Choi, J.-W.; Paik, D.-S.; Yoon, S.-J. Issue and Challenges Facing Rechargeable Thin Film Lithium Batteries. Mater. Res. Bull. 2008, 43 (8), 19131942,  DOI: 10.1016/j.materresbull.2007.08.031
  16. 16
    McCloskey, B. D. Attainable Gravimetric and Volumetric Energy Density of Li–S and Li Ion Battery Cells with Solid Separator-Protected Li Metal Anodes. J. Phys. Chem. Lett. 2015, 6 (22), 45814588,  DOI: 10.1021/acs.jpclett.5b01814
  17. 17
    Gutiérrez-Pardo, A.; Pitillas Martinez, A. I.; Otaegui, L.; Schneider, M.; Roters, A.; Llordés, A.; Aguesse, F.; Buannic, L. Will the Competitive Future of Solid State Li Metal Batteries Rely on a Ceramic or a Composite Electrolyte?. Sustainable Energy Fuels 2018, 2 (10), 23252334,  DOI: 10.1039/C8SE00273H
  18. 18
    Pfenninger, R.; Struzik, M.; Garbayo, I.; Stilp, E.; Rupp, J. L. M. A Low Ride on Processing Temperature for Fast Lithium Conduction in Garnet Solid-State Battery Films. Nat. Energy 2019, 4 (6), 475483,  DOI: 10.1038/s41560-019-0384-4
  19. 19
    Chan, C.; Yang, T.; Weller, J. M. Nanostructured Garnet-type Li7La3Zr2O12: Synthesis, Properties, and Opportunities as Electrolytes for Li-ion Batteries. Electrochim. Acta 2017, 253, 268280,  DOI: 10.1016/j.electacta.2017.08.130
  20. 20
    Wang, B.; Chakoumakos, B. C.; Sales, B. C.; Kwak, B. S.; Bates, J. B. Synthesis, Crystal Structure, and Ionic Conductivity of a Polycrystalline Lithium Phosphorus Oxynitride with the γ-Li3PO4 Structure. J. Solid State Chem. 1995, 115 (2), 313323,  DOI: 10.1006/jssc.1995.1140
  21. 21
    Senevirathne, K.; Day, C. S.; Gross, M. D.; Lachgar, A.; Holzwarth, N. A. W. A New Crystalline LiPON Electrolyte: Synthesis, Properties, and Electronic Structure. Solid State Ionics 2013, 233, 95101,  DOI: 10.1016/j.ssi.2012.12.013
  22. 22
    Baur, W. H.; Ohta, T. The Crystal Structure of Li3.75Si0.75P0.25O4 and Ionic Conductivity in Tetrahedral Structures. J. Solid State Chem. 1982, 44 (1), 5059,  DOI: 10.1016/0022-4596(82)90400-5
  23. 23
    Ayu, N. I. P.; Kartini, E.; Prayogi, L. D.; Faisal, M.; Supardi Crystal Structure Analysis of Li3PO4 Powder Prepared by Wet Chemical Reaction and Solid-State Reaction by Using X-Ray Diffraction (XRD). Ionics 2016, 22 (7), 10511057,  DOI: 10.1007/s11581-016-1643-z
  24. 24
    Lee, C.; Dutta, P. K.; Ramamoorthy, R.; Akbar, S. A. Mixed Ionic and Electronic Conduction in Li3PO4 Electrolyte for a CO2 Gas Sensor. J. Electrochem. Soc. 2006, 153 (1), H4H14,  DOI: 10.1149/1.2129180
  25. 25
    Takada, K. Progress and Prospective of Solid-State Lithium Batteries. Acta Mater. 2013, 61 (3), 759770,  DOI: 10.1016/j.actamat.2012.10.034
  26. 26
    Wang, B.; Kwak, B. S.; Sales, B. C.; Bates, J. B. Ionic Conductivities and Structure of Lithium Phosphorus Oxynitride Glasses. J. Non-Cryst. Solids 1995, 183 (3), 297306,  DOI: 10.1016/0022-3093(94)00665-2
  27. 27
    Lacivita, V.; Westover, A. S.; Kercher, A.; Phillip, N. D.; Yang, G.; Veith, G.; Ceder, G.; Dudney, N. J. Resolving the Amorphous Structure of Lithium Phosphorus Oxynitride (Lipon). J. Am. Chem. Soc. 2018, 140 (35), 1102911038,  DOI: 10.1021/jacs.8b05192
  28. 28
    Urbanovich, V. S. Computerized System for the Sintering of Nanoceramics at High Pressures. Powder Metall. Met. Ceram. 2003, 42 (1), 1923,  DOI: 10.1023/A:1023986831049
  29. 29
    Galceran, M.; Pujol, M. C.; Gluchowski, P.; Strȩk, W.; Carvajal, J. J.; Mateos, X.; Aguiló, M.; Díaz, F. A Promising Lu2–xHoxO3 Laser Nanoceramic: Synthesis and Characterization. J. Am. Ceram. Soc. 2010, 93 (11), 37643772,  DOI: 10.1111/j.1551-2916.2010.03924.x
  30. 30
    Inada, R.; Yasuda, S.; Tojo, M.; Tsuritani, T.; Tojo, T.; Sakurai, Y. Development of Lithium-Stuffed Garnet-Type Oxide Solid Electrolytes with High Ionic Conductivity for Application to All-Solid-State Batteries. Front. Energy Res. 2016, 4, 28,  DOI: 10.3389/fenrg.2016.00028
  31. 31
    Wang, B.; Chakoumakos, B. C.; Sales, B. C.; Kwak, B. S.; Bates, J. B. Synthesis, Crystal Structure, and Ionic Conductivity of a Polycrystalline Lithium Phosphorus Oxynitride with the γ-Li3PO4 Structure. J. Solid State Chem. 1995, 115 (2), 313323,  DOI: 10.1006/jssc.1995.1140
  32. 32
    West, W. C.; Whitacre, J. F.; Lim, J. R. Chemical Stability Enhancement of Lithium Conducting Solid Electrolyte Plates Using Sputtered LiPON Thin Films. J. Power Sources 2004, 126 (1), 134138,  DOI: 10.1016/j.jpowsour.2003.08.030
  33. 33
    Dudney, N. J. Addition of a Thin-Film Inorganic Solid Electrolyte (Lipon) as a Protective Film in Lithium Batteries with a Liquid Electrolyte. J. Power Sources 2000, 89 (2), 176179,  DOI: 10.1016/S0378-7753(00)00427-4
  34. 34
    Visco, S. J.; Chu, M.-Y. Protective Coatings for Negative Electrodes. U.S. Patent No. US6025094A, Feb. 15, 2000.
  35. 35
    Put, B.; Vereecken, P. M.; Stesmans, A. On the Chemistry and Electrochemistry of LiPON Breakdown. J. Mater. Chem. A 2018, 6 (11), 48484859,  DOI: 10.1039/C7TA07928A
  36. 36
    Li, J.; Ma, C.; Chi, M.; Liang, C.; Dudney, N. J. Solid Electrolyte: The Key for High-Voltage Lithium Batteries. Adv. Energy Mater. 2015, 5 (4), 14014081401416,  DOI: 10.1002/aenm.201401408
  37. 37
    Famprikis, T.; Canepa, P.; Dawson, J. A.; Islam, M. S.; Masquelier, C. Fundamentals of Inorganic Solid-State Electrolytes for Batteries. Nat. Mater. 2019, 18, 12781291,  DOI: 10.1038/s41563-019-0431-3
  38. 38
    Alexander, G. V.; Patra, S.; Sobhan Raj, S. V.; Sugumar, M. K.; Ud Din, M. M.; Murugan, R. Electrodes-Electrolyte Interfacial Engineering for Realizing Room Temperature Lithium Metal Battery Based on Garnet Structured Solid Fast Li+ Conductors. J. Power Sources 2018, 396, 764773,  DOI: 10.1016/j.jpowsour.2018.06.096
  39. 39
    Tsai, C.-L.; Roddatis, V.; Chandran, C. V.; Ma, Q.; Uhlenbruck, S.; Bram, M.; Heitjans, P.; Guillon, O. Li7La3Zr2O12 Interface Modification for Li Dendrite Prevention. ACS Appl. Mater. Interfaces 2016, 8 (16), 1061710626,  DOI: 10.1021/acsami.6b00831

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  • Abstract

    Figure 1

    Figure 1. (a) Expected theoretical gravimetric and volumetric energy densities (Eg and Ev, respectively) of high-voltage Li-metal SSBs, as a function of the cathode loading and including LiPON, LATP, or LLZO as SEs. (b) Schematic representation of the cell model considered for the theoretical predictions shown in panel (a).

    Figure 2

    Figure 2. Results of the combined Rietveld refinement of (a) the XRD pattern and (b) the NPD pattern of b-Li3.6PO3.4N0.6. (c) Representation of the refined structure. The six Li positions are shown as purple and white balls, indicating the partial occupation of each site. Positions of P, O, and N are shown as green, orange, and blue balls, respectively, forming tetrahedral cationic sites drawn in green pointing in opposite directions (up–down pattern). (d) 7Li and 31P solid-state MAS NMR spectra of b- Li3.6PO3.4N0.6. One average signal is observed for the Li, while three distinct environments are clearly observed for the P. The attribution and quantification of these three fitted peaks are indicated.

    Figure 3

    Figure 3. (a) Ionic conductivity as a function of the temperature for a b-Li3.6PO3.4N0.6 pellet prepared by HPLT at 5.5 GPa and 200 °C. (b) Cyclic voltammetry of b-Li3.6PO3.4N0.6 acquired at 0.5 mV s–1 in the −0.15–5 V vs Li+/Li0 for two cycles. (c) Stripping and plating experiment of a symmetric Li|b-Li3.6PO3.4N0.6|Li cell at 70 °C (inset shows data between 50 h and 70 h).

  • References

    ARTICLE SECTIONS
    Jump To

    This article references 39 other publications.

    1. 1
      Yu, X.; Bates, J. B.; Jellison, G. E.; Hart, F. X. A Stable Thin-Film Lithium Electrolyte: Lithium Phosphorus Oxynitride. J. Electrochem. Soc. 1997, 144 (2), 524532,  DOI: 10.1149/1.1837443
    2. 2
      Bates, J. B.; Dudney, N. J.; Gruzalski, G. R.; Zuhr, R. A.; Choudhury, A.; Luck, C. F.; Robertson, J. D. Fabrication and Characterization of Amorphous Lithium Electrolyte Thin Films and Rechargeable Thin-Film Batteries. J. Power Sources 1993, 43 (1), 103110,  DOI: 10.1016/0378-7753(93)80106-Y
    3. 3
      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, 647654,  DOI: 10.1016/0167-2738(92)90442-R
    4. 4
      Oudenhoven, J. F. M.; Baggetto, L.; Notten, P. H. L. All-Solid-State Lithium-Ion Microbatteries: A Review of Various Three-Dimensional Concepts. Adv. Energy Mater. 2011, 1 (1), 1033,  DOI: 10.1002/aenm.201000002
    5. 5
      Nowak, S.; Berkemeier, F.; Schmitz, G. Ultra-Thin LiPON Films – Fundamental Properties and Application in Solid State Thin Film Model Batteries. J. Power Sources 2015, 275, 144150,  DOI: 10.1016/j.jpowsour.2014.10.202
    6. 6
      Zheng, F.; Kotobuki, M.; Song, S.; Lai, M. O.; Lu, L. Review on Solid Electrolytes for All-Solid-State Lithium-Ion Batteries. J. Power Sources 2018, 389, 198213,  DOI: 10.1016/j.jpowsour.2018.04.022
    7. 7
      Albertus, P.; Babinec, S.; Litzelman, S.; Newman, A. Status and Challenges in Enabling the Lithium Metal Electrode for High-Energy and Low-Cost Rechargeable Batteries. Nat. Energy 2018, 3 (1), 1621,  DOI: 10.1038/s41560-017-0047-2
    8. 8
      Gao, Z.; Sun, H.; Fu, L.; Ye, F.; Zhang, Y.; Luo, W.; Huang, Y. Promises, Challenges, and Recent Progress of Inorganic Solid-State Electrolytes for All-Solid-State Lithium Batteries. Adv. Mater. 2018, 30, 1870122,  DOI: 10.1002/adma.201870122
    9. 9
      Schnell, J.; Günther, T.; Knoche, T.; Vieider, C.; Köhler, L.; Just, A.; Keller, M.; Passerini, S.; Reinhart, G. All-Solid-State Lithium-Ion and Lithium Metal Batteries – Paving the Way to Large-Scale Production. J. Power Sources 2018, 382, 160175,  DOI: 10.1016/j.jpowsour.2018.02.062
    10. 10
      Janek, J.; Zeier, W. G. A Solid Future for Battery Development. Nature Energy 2016, 1, 1614116144,  DOI: 10.1038/nenergy.2016.141
    11. 11
      Cheng, D.; Wynn, T. A.; Wang, X.; Wang, S.; Zhang, M.; Shimizu, R.; Bai, S.; Nguyen, H.; Fang, C.; Kim, M.; Li, W.; Lu, B.; Kim, S. J.; Meng, Y. S. Unveiling the Stable Nature of the Solid Electrolyte Interphase between Lithium Metal and LiPON via Cryogenic Electron Microscopy. Joule 2020, 4 (11), P2484P2500,  DOI: 10.2139/ssrn.3640837
    12. 12
      Wang, M. J.; Carmona, E.; Gupta, A.; Albertus, P.; Sakamoto, J. Enabling “Lithium-Free” Manufacturing of Pure Lithium Metal Solid-State Batteries through in Situ Plating. Nat. Commun. 2020, 11 (1), 52015209,  DOI: 10.1038/s41467-020-19004-4
    13. 13
      Neudecker, B. J.; Dudney, N. J.; Bates, J. B. Lithium-Free” Thin-Film Battery with In Situ Plated Li Anode. J. Electrochem. Soc. 2000, 147 (2), 517523,  DOI: 10.1149/1.1393226
    14. 14
      Bates, J. B.; Dudney, N. J.; Neudecker, B.; Ueda, A.; Evans, C. D. Thin-Film Lithium and Lithium-Ion Batteries. Solid State Ionics 2000, 135 (1), 3345,  DOI: 10.1016/S0167-2738(00)00327-1
    15. 15
      Patil, A.; Patil, V.; Wook Shin, D.; Choi, J.-W.; Paik, D.-S.; Yoon, S.-J. Issue and Challenges Facing Rechargeable Thin Film Lithium Batteries. Mater. Res. Bull. 2008, 43 (8), 19131942,  DOI: 10.1016/j.materresbull.2007.08.031
    16. 16
      McCloskey, B. D. Attainable Gravimetric and Volumetric Energy Density of Li–S and Li Ion Battery Cells with Solid Separator-Protected Li Metal Anodes. J. Phys. Chem. Lett. 2015, 6 (22), 45814588,  DOI: 10.1021/acs.jpclett.5b01814
    17. 17
      Gutiérrez-Pardo, A.; Pitillas Martinez, A. I.; Otaegui, L.; Schneider, M.; Roters, A.; Llordés, A.; Aguesse, F.; Buannic, L. Will the Competitive Future of Solid State Li Metal Batteries Rely on a Ceramic or a Composite Electrolyte?. Sustainable Energy Fuels 2018, 2 (10), 23252334,  DOI: 10.1039/C8SE00273H
    18. 18
      Pfenninger, R.; Struzik, M.; Garbayo, I.; Stilp, E.; Rupp, J. L. M. A Low Ride on Processing Temperature for Fast Lithium Conduction in Garnet Solid-State Battery Films. Nat. Energy 2019, 4 (6), 475483,  DOI: 10.1038/s41560-019-0384-4
    19. 19
      Chan, C.; Yang, T.; Weller, J. M. Nanostructured Garnet-type Li7La3Zr2O12: Synthesis, Properties, and Opportunities as Electrolytes for Li-ion Batteries. Electrochim. Acta 2017, 253, 268280,  DOI: 10.1016/j.electacta.2017.08.130
    20. 20
      Wang, B.; Chakoumakos, B. C.; Sales, B. C.; Kwak, B. S.; Bates, J. B. Synthesis, Crystal Structure, and Ionic Conductivity of a Polycrystalline Lithium Phosphorus Oxynitride with the γ-Li3PO4 Structure. J. Solid State Chem. 1995, 115 (2), 313323,  DOI: 10.1006/jssc.1995.1140
    21. 21
      Senevirathne, K.; Day, C. S.; Gross, M. D.; Lachgar, A.; Holzwarth, N. A. W. A New Crystalline LiPON Electrolyte: Synthesis, Properties, and Electronic Structure. Solid State Ionics 2013, 233, 95101,  DOI: 10.1016/j.ssi.2012.12.013
    22. 22
      Baur, W. H.; Ohta, T. The Crystal Structure of Li3.75Si0.75P0.25O4 and Ionic Conductivity in Tetrahedral Structures. J. Solid State Chem. 1982, 44 (1), 5059,  DOI: 10.1016/0022-4596(82)90400-5
    23. 23
      Ayu, N. I. P.; Kartini, E.; Prayogi, L. D.; Faisal, M.; Supardi Crystal Structure Analysis of Li3PO4 Powder Prepared by Wet Chemical Reaction and Solid-State Reaction by Using X-Ray Diffraction (XRD). Ionics 2016, 22 (7), 10511057,  DOI: 10.1007/s11581-016-1643-z
    24. 24
      Lee, C.; Dutta, P. K.; Ramamoorthy, R.; Akbar, S. A. Mixed Ionic and Electronic Conduction in Li3PO4 Electrolyte for a CO2 Gas Sensor. J. Electrochem. Soc. 2006, 153 (1), H4H14,  DOI: 10.1149/1.2129180
    25. 25
      Takada, K. Progress and Prospective of Solid-State Lithium Batteries. Acta Mater. 2013, 61 (3), 759770,  DOI: 10.1016/j.actamat.2012.10.034
    26. 26
      Wang, B.; Kwak, B. S.; Sales, B. C.; Bates, J. B. Ionic Conductivities and Structure of Lithium Phosphorus Oxynitride Glasses. J. Non-Cryst. Solids 1995, 183 (3), 297306,  DOI: 10.1016/0022-3093(94)00665-2
    27. 27
      Lacivita, V.; Westover, A. S.; Kercher, A.; Phillip, N. D.; Yang, G.; Veith, G.; Ceder, G.; Dudney, N. J. Resolving the Amorphous Structure of Lithium Phosphorus Oxynitride (Lipon). J. Am. Chem. Soc. 2018, 140 (35), 1102911038,  DOI: 10.1021/jacs.8b05192
    28. 28
      Urbanovich, V. S. Computerized System for the Sintering of Nanoceramics at High Pressures. Powder Metall. Met. Ceram. 2003, 42 (1), 1923,  DOI: 10.1023/A:1023986831049
    29. 29
      Galceran, M.; Pujol, M. C.; Gluchowski, P.; Strȩk, W.; Carvajal, J. J.; Mateos, X.; Aguiló, M.; Díaz, F. A Promising Lu2–xHoxO3 Laser Nanoceramic: Synthesis and Characterization. J. Am. Ceram. Soc. 2010, 93 (11), 37643772,  DOI: 10.1111/j.1551-2916.2010.03924.x
    30. 30
      Inada, R.; Yasuda, S.; Tojo, M.; Tsuritani, T.; Tojo, T.; Sakurai, Y. Development of Lithium-Stuffed Garnet-Type Oxide Solid Electrolytes with High Ionic Conductivity for Application to All-Solid-State Batteries. Front. Energy Res. 2016, 4, 28,  DOI: 10.3389/fenrg.2016.00028
    31. 31
      Wang, B.; Chakoumakos, B. C.; Sales, B. C.; Kwak, B. S.; Bates, J. B. Synthesis, Crystal Structure, and Ionic Conductivity of a Polycrystalline Lithium Phosphorus Oxynitride with the γ-Li3PO4 Structure. J. Solid State Chem. 1995, 115 (2), 313323,  DOI: 10.1006/jssc.1995.1140
    32. 32
      West, W. C.; Whitacre, J. F.; Lim, J. R. Chemical Stability Enhancement of Lithium Conducting Solid Electrolyte Plates Using Sputtered LiPON Thin Films. J. Power Sources 2004, 126 (1), 134138,  DOI: 10.1016/j.jpowsour.2003.08.030
    33. 33
      Dudney, N. J. Addition of a Thin-Film Inorganic Solid Electrolyte (Lipon) as a Protective Film in Lithium Batteries with a Liquid Electrolyte. J. Power Sources 2000, 89 (2), 176179,  DOI: 10.1016/S0378-7753(00)00427-4
    34. 34
      Visco, S. J.; Chu, M.-Y. Protective Coatings for Negative Electrodes. U.S. Patent No. US6025094A, Feb. 15, 2000.
    35. 35
      Put, B.; Vereecken, P. M.; Stesmans, A. On the Chemistry and Electrochemistry of LiPON Breakdown. J. Mater. Chem. A 2018, 6 (11), 48484859,  DOI: 10.1039/C7TA07928A
    36. 36
      Li, J.; Ma, C.; Chi, M.; Liang, C.; Dudney, N. J. Solid Electrolyte: The Key for High-Voltage Lithium Batteries. Adv. Energy Mater. 2015, 5 (4), 14014081401416,  DOI: 10.1002/aenm.201401408
    37. 37
      Famprikis, T.; Canepa, P.; Dawson, J. A.; Islam, M. S.; Masquelier, C. Fundamentals of Inorganic Solid-State Electrolytes for Batteries. Nat. Mater. 2019, 18, 12781291,  DOI: 10.1038/s41563-019-0431-3
    38. 38
      Alexander, G. V.; Patra, S.; Sobhan Raj, S. V.; Sugumar, M. K.; Ud Din, M. M.; Murugan, R. Electrodes-Electrolyte Interfacial Engineering for Realizing Room Temperature Lithium Metal Battery Based on Garnet Structured Solid Fast Li+ Conductors. J. Power Sources 2018, 396, 764773,  DOI: 10.1016/j.jpowsour.2018.06.096
    39. 39
      Tsai, C.-L.; Roddatis, V.; Chandran, C. V.; Ma, Q.; Uhlenbruck, S.; Bram, M.; Heitjans, P.; Guillon, O. Li7La3Zr2O12 Interface Modification for Li Dendrite Prevention. ACS Appl. Mater. Interfaces 2016, 8 (16), 1061710626,  DOI: 10.1021/acsami.6b00831
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    • Parameters for theoretical calculations, experimental methods, and additional figures (PDF)

    • Crystal structure of b-Li3.6PO3.4N0.6, as determined via NPD (CIF)

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