Interfacial reactivity and interphase growth of argyrodite solid electrolytes at lithium metal electrodes

Wenzel, Sibylle; Sedlmaier, Stefan J.; Dietrich, Christian; Zeier, Wolfgang G.; Janek, Jürgen

doi:10.1016/j.ssi.2017.07.005

Cited by 447 publications

(549 citation statements)

References 26 publications

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“…Hence, such nitrides seem to exhibit significantly higher stability with respect to Li metal compared to oxides (Li 3 PO 4 : cathodic limit with respectt oL i/Li + 0.69 V),s ulfides (Li 3 PS 4 : 1.72 V), and halides( LiPF 6 :2 .74 V). [27] To avoid continuous decomposition by Li metal, the use of only non-metal elements (P,C l, Br,I )has been discussed, because they form passivating interphases (solid electrolyte interphases,S EI), which again enable stabilityw ith respectt oL im etal, such as in LiPON, argyrodites, [28] or Li 3 OCl/Li 3 OBr. [27] Three ternary lithium nitridophosphates have hitherto been investigated with regard to their ion conductivity:L i 7 PN 4 (1.7 10 À5 W À1 cm À1 at 125 8C, 0.49 eV), [29] Li 18 P 6 N 16 (1.5 10 À5 W À1 cm À1 at 125 8C, 0.50 eV), [24] and LiPN 2 (6.8 10 À7 W À1 cm À1 at 125 8C, 0.61 eV).…”

Section: Introductionmentioning

confidence: 99%

Li⁺ Ion Conductors with Adamantane‐Type Nitridophosphate Anions β‐Li₁₀P₄N₁₀ and Li₁₃P₄N₁₀X₃ with X=Cl, Br

Bertschler

Dietrich

Leichtweiß

et al. 2017

Chemistry A European J

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b-Li 10 P 4 N 10 and Li 13 P 4 N 10 X 3 with X = Cl, Br have been synthesized from mixtures of P 3 N 5 ,L i 3 N, LiX,L iPN 2 ,a nd Li 7 PN 4 at temperatures below 850 8C. b-Li 10 P 4 N 10 is the lowtemperature polymorph of a-Li 10 P 4 N 10 and crystallizes in the trigonal space group R3. It is made up of non-condensed [P 4 N 10 ] 10À T2 supertetrahedra, whicha re arrangedi ns phalerite-analogous packing. Li 13 P 4 N 10 X 3 (X = Cl, Br) crystallizes in the cubic space group Fm " 3m.B oth isomorphic compounds comprise adamantane-type [P 4 N 10 ] 10À ,L i + ions, and halides, which form octahedra. These octahedra build up af ace-centered cubic packing,w hose tetrahedral voids are occupied by the [P 4 N 10 ] 10À ions. The crystal structures have been elucidated from X-ray powder diffraction data and corroborated by EDX measurements, solid-state NMR, and FTIR spectroscopy.F urthermore,w eh ave examined the phase transition between a-a nd b-Li 10 P 4 N 10 .T oc onfirm the ionic character, the migration pathways of the Li + ions have been evaluated and the ion conductivity and its temperature dependence have been determined by impedance spectroscopy.X PS measurementsh aveb een carriedo ut to analyze the stability with respect to Li metal.

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Section: Introductionmentioning

confidence: 99%

Li⁺ Ion Conductors with Adamantane‐Type Nitridophosphate Anions β‐Li₁₀P₄N₁₀ and Li₁₃P₄N₁₀X₃ with X=Cl, Br

Bertschler

Dietrich

Leichtweiß

et al. 2017

Chemistry A European J

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“…[177,184,187] The Li 2 S has an ionic conductivity of only 10 nS cm −1 , [181] which is extremely lower than the ionic conductivity of the LGPS (≈10 −2 S cm −1 ), Li 2 S-P 2 S 5 (10 −3 -10 −2 S cm −1 ), and Li 6 PS 5 X (10 −4 -10 −3 S cm −1 ). [184] Third, wettability between the SSEs and Li will also affect the interfacial impedance. Second, the SEI layer still continues to grow, and even reaction products within the layer have a limited electronic conductivity.…”

Section: Sulfidementioning

confidence: 95%

“…Type II (Figure 8b): the SSEs are thermodynamically unstable against Li, and Li insertion will produce mixed ionic-electronic conducting interphases with both reasonably high ionic and electronic conductivity. [184] Copyright 2018, Elsevier. The SSEs containing multivalent cations, i.e., NASICON-type LATP/LAGP and perovskite-type LLTO, are prone to produce such kind of interphases.…”

Section: Origin Of the Interfacial Resistancementioning

confidence: 99%

“…LGPS Li 2 S, Li 3 P and Ge/Li 15 Ge 4 [177] In situ XPS Type II Operando XPS Type III Li 3 N No reaction [177,178] Type I LiPON Li 3 PO 4 , Li 3 P, Li 3 N and Li 2 O [180] In situ XPS Type III Li 6 PS 5 X Li 3 P, Li 2 S and LiX [184] In situ XPS Type III LLZO having a total ionic conductivity of ≈2.3 × 10 −5 S cm −1 , [185] whereas the ionic conductivity for pristine cubic LLZO is ≈10 −4 S cm −1 . The Li 2 S is the primary phase in the SEI layer for the LGPS, Li 2 S-P 2 S 5 , and Li 6 PS 5 X.…”

Section: Sulfidementioning

confidence: 99%

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Interfacial Incompatibility and Internal Stresses in All‐Solid‐State Lithium Ion Batteries

Liu

et al. 2019

Advanced Energy Materials

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The continuous depletion of fossil fuels, the increase of oil prices, and the need to decrease CO 2 emissions have stimulated intensive research on developing alternative renewable and clean energy sources. [1] Among these alternative energy sources, rechargeable Li-ion batteries (LIBs) are one of the promising candidates. To date, the LIBs basically consisting of a positive electrode (cathode), an electrolyte, and a negative electrode (anode) have widespread applications, such as portable electronic devices, pure electric vehicles (PEVs), and hybrid electric vehicles (HEVs). [2] The state-of-the-art electrolytes are usually the lithium salts (LiPF 6 , LiBF 4 , and LiCF 3 SO 3 ) dissolved in organic solvents, i.e., ethylene carbonate, propylene carbonate, polyethylene oxide, and dimethyl carbonate, [3] which exhibit excellent wetting of the electrodes and produce a fast transfer of Li + ions upon charging and discharging. However, they suffer from flammability, poor electrochemical stability, limited temperature range of operation, and low power density. [4] There is an ever-increasing demand for batteries with a higher energy and power density, although current LIBs offer volumetric and gravimetric energy densities up to 770 Wh L −1 and 260 Wh kg −1 , respectively. [5] To improve the energy/power density of LIBs, one way is to adopt high-potential cathode materials such as LiNi 0.5 Mn 1.5 O 4 (LNMO). The high-voltage plateau of LNMO (≈4.7 V vs Li/Li + ) makes its energy density 20-30% higher than the energy density of commercial LiCoO 2 and LiFePO 4 . [6] However, successful commercialization of the LNMO is restricted in high-energy LIBs due to electrolyte decomposition and side reaction of the cathodes and liquid electrolytes when operating at high voltages. [7,8] The other way to improve the energy/power density is to replace the conventional graphite anode with Li metal. The Li metal, with a low anode potential (−3.04 V vs standard hydrogen electrode) and high specific capacity (3862 mAh g −1 for the Li anode versus 372 mAh g −1 for the graphite anode), [9][10][11] has been considered as the "Holy Grail" of battery technologies. When paired with sulfur and oxygen, the theoretical energy density of Li-S (≈2567 Wh kg −1 ) and Li-O 2 (≈3505 Wh kg −1 ) batteries is far higher than the theoretical energy density of conventional LIBs (≈387 Wh kg −1 ). [12][13][14][15] When Li metal approaches the liquid electrolytes, however, unstable Li/electrolyte interface Rechargeable Li-ion batteries (LIBs) are electrochemical storage device widely applied in electric vehicles, mobile electronic devices, etc. However, traditional LIBs containing liquid electrolytes suffer from flammability, poor electrochemical stability, and limited operational temperature range. Replacement of the liquid electrolytes with inorganic solid-state electrolytes (SSEs) would solve this problem. However, several critical issues, such as poor interfacial compatibility, low ionic conductivity at ambient temperatures, etc., need to be surmounted befor...

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“…To date, graphite, graphite–silicon composite, and lithium metal anode, which have been studied in conventional LIBs using a liquid electrolyte, have been utilized as anode materials in ASSLBs . Among the various anode materials, lithium metal has been extensively investigated in ASSLBs because of the mitigated formation of metallic lithium and volume expansion, compared with the conventional LIBs.…”

Section: Recent Progress In Electrode Materialsmentioning

confidence: 99%

Advances and Prospects of Sulfide All‐Solid‐State Lithium Batteries via One‐to‐One Comparison with Conventional Liquid Lithium Ion Batteries

et al. 2019

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Owing to the safety issue of lithium ion batteries (LIBs) under the harsh operating conditions of electric vehicles and mobile devices, all‐solid‐state lithium batteries (ASSLBs) that utilize inorganic solid electrolytes are regarded as a secure next‐generation battery system. Significant efforts are devoted to developing each component of ASSLBs, such as the solid electrolyte and the active materials, which have led to considerable improvements in their electrochemical properties. Among the various solid electrolytes such as sulfide, polymer, and oxide, the sulfide solid electrolyte is considered as the most promising candidate for commercialization because of its high lithium ion conductivity and mechanical properties. However, the disparity in energy and power density between the current sulfide ASSLBs and conventional LIBs is still wide, owing to a lack of understanding of the battery electrode system. Representative developments of ASSLBs in terms of the sulfide solid electrolyte, active materials, and electrode engineering are presented with emphasis on the current status of their electrochemical performances, compared to those of LIBs. As a rational method to realizing high energy sulfide ASSLBs, the requirements for the sulfide solid electrolytes and active materials are provided along through simple experimental demonstrations. Potential future research directions in the development of commercially viable sulfide ASSLBs are suggested.

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Interfacial reactivity and interphase growth of argyrodite solid electrolytes at lithium metal electrodes

Cited by 447 publications

References 26 publications

Li⁺ Ion Conductors with Adamantane‐Type Nitridophosphate Anions β‐Li₁₀P₄N₁₀ and Li₁₃P₄N₁₀X₃ with X=Cl, Br

Li⁺ Ion Conductors with Adamantane‐Type Nitridophosphate Anions β‐Li₁₀P₄N₁₀ and Li₁₃P₄N₁₀X₃ with X=Cl, Br

Interfacial Incompatibility and Internal Stresses in All‐Solid‐State Lithium Ion Batteries

Advances and Prospects of Sulfide All‐Solid‐State Lithium Batteries via One‐to‐One Comparison with Conventional Liquid Lithium Ion Batteries

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Interfacial reactivity and interphase growth of argyrodite solid electrolytes at lithium metal electrodes

Cited by 447 publications

References 26 publications

Li+ Ion Conductors with Adamantane‐Type Nitridophosphate Anions β‐Li10P4N10 and Li13P4N10X3 with X=Cl, Br

Li+ Ion Conductors with Adamantane‐Type Nitridophosphate Anions β‐Li10P4N10 and Li13P4N10X3 with X=Cl, Br

Interfacial Incompatibility and Internal Stresses in All‐Solid‐State Lithium Ion Batteries

Advances and Prospects of Sulfide All‐Solid‐State Lithium Batteries via One‐to‐One Comparison with Conventional Liquid Lithium Ion Batteries

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Li⁺ Ion Conductors with Adamantane‐Type Nitridophosphate Anions β‐Li₁₀P₄N₁₀ and Li₁₃P₄N₁₀X₃ with X=Cl, Br

Li⁺ Ion Conductors with Adamantane‐Type Nitridophosphate Anions β‐Li₁₀P₄N₁₀ and Li₁₃P₄N₁₀X₃ with X=Cl, Br