Lithium Argyrodite as Solid Electrolyte and Cathode Precursor for Solid‐State Batteries with Long Cycle Life

Wang, Shuo; Tang, Mingxue; Zhang, Qinghua; Li, Baohua; Ohno, Saneyuki; Walther, Felix; Pan, Ruijun; Xu, Xiangyang; Xin, Chengzhou; Zhang, Wenbo; Li, Liangliang; Shen, Yang; Richter, Felix H.; Janek, Jürgen; Nan, Ce Wen

doi:10.1002/aenm.202101370

Cited by 65 publications

(66 citation statements)

References 59 publications

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“…The cell volume expands during the discharge process resulting in a net pressure of ≈0.5 MPa, which is comparable to the conventional cathode materials reports in sulfide‐based all‐solid‐state systems. [ 45 ] Thus, to alleviate the compressive stress and maintain interfacial contact, an external pressure of about 300 MPa was for the electrochemical performance tests of the all‐solid‐state Se–LHC–C/LHC/Li cell. In contrast, the electrochemical behavior without externally applied pressure is also shown in Figure S17, Supporting Information.…”

Section: Resultsmentioning

confidence: 99%

Highly Stable Halide‐Electrolyte‐Based All‐Solid‐State Li–Se Batteries

Liang

Kim

et al. 2022

Advanced Materials

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Solid‐state Li–S and Li–Se batteries are promising devices that can address the safety and electrochemical stability issues that arise from liquid‐based systems. However, solid‐state Li–Se/S batteries usually present poor cycling stability due to the high resistance interfaces and decomposition of solid electrolytes caused by their narrow electrochemical stability windows. Here, an integrated solid‐state Li–Se battery based on a halide Li3HoCl6 solid electrolyte with high ionic conductivity is presented. The intrinsic wide electrochemical stability window of the Li3HoCl6 and its stability toward Se and the lithiated species effectively inhibit degeneration of the electrolyte and the Se cathode by suppressing side reactions. The inherent thermodynamic mechanism of the lithiation/delithiation process of the Se cathode in solid is also revealed and confirmed by theoretical calculations. The battery achieves a reversible capacity of 402 mAh g−1 after 750 cycles. The electrochemical performance, thermodynamic lithiation/delithiation mechanism, and stability of metal‐halide‐based Li–Se batteries confer theoretical study and practical applicability that extends to other energy‐storage systems.

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Section: Resultsmentioning

confidence: 99%

Highly Stable Halide‐Electrolyte‐Based All‐Solid‐State Li–Se Batteries

Liang

Kim

et al. 2022

Advanced Materials

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“…Other sulfide SEs also have been found to have similar reversible properties, such as Li 3 PS 4 , 78Li 2 S Á 22P 2 S 5 , LGPS, and Li 6 PS 5 Cl 0.5 Br 0.5 . 65,[152][153][154][155][156][157] In addition to the self-decomposition, the sulfides are also (electro-)chemically unstable to some CAMs (e.g., LiCoO 2 ) due to the mismatch chemical potential. 158 As illustrated in Figure 4F, in the case of the Fermi energy level of the cathode (μ c ) below the electrolyte HOMO, the electrolytes undergo oxidation at the cathode interfaces and thereby form cathode electrolyte interphases (CEI); in contrast, an anode with a μ a above the electrolyte LUMO will reduce the electrolyte to form solid electrolyte interphases (SEI).…”

Section: The Electrochemical Reaction Occurs At Interfacesmentioning

confidence: 99%

“…However, Dewald et al 151 assumed that the formation of crystalline P 2 S 5 was not feasible due to entropic reasons, while the local formation of bridging sulfur (i.e., P–S x –P bonds) was more likely to occur. In addition, Wang et al 152 found that PS 4 3− will convert into P 2 S 7 4− and S (0) , and finally to P 2 S 6 2− and S (0) . Other sulfide SEs also have been found to have similar reversible properties, such as Li 3 PS 4 , 78Li 2 S · 22P 2 S 5 , LGPS, and Li 6 PS 5 Cl 0.5 Br 0.5 65,152–157 …”

Section: Interfacial Issuesmentioning

confidence: 99%

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Challenges, interface engineering, and processing strategies toward practical sulfide‐based all‐solid‐state lithium batteries

Liang

Liu

Wang

et al. 2022

InfoMat

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106

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All‐solid‐state lithium batteries have emerged as a priority candidate for the next generation of safe and energy‐dense energy storage devices surpassing state‐of‐art lithium‐ion batteries. Among multitudinous solid‐state batteries based on solid electrolytes (SEs), sulfide SEs have attracted burgeoning scrutiny due to their superior ionic conductivity and outstanding formability. However, from the perspective of their practical applications concerning cell integration and production, it is still extremely challenging to constructing compatible electrolyte/electrode interfaces and developing available scale processing technologies. This review presents a critical overview of the current underlying understanding of interfacial issues and analyzes the main processing challenges faced by sulfide‐based all‐solid‐state batteries from the aspects of cost‐effective and energy‐dense design. Besides, the corresponding approaches involving interface engineering and processing protocols for addressing these issues and challenges are summarized. Fundamental and engineering perspectives on future development avenues toward practical application of high energy, safety, and long‐life sulfide‐based all‐solid‐state batteries are ultimately provided.

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“…Once the peaks (★ and ☆) appear, their magnitude increases with further SE oxidation (orange to red curves). The oxidative degradation of Li-thiophosphates leads to amorphous phases with complex P-[S] n -P-type polyanions, e.g., (P 2 S n ), Li 2 S n , Li 3 PS 4 (μ-S n )S 4 PLi 3 ((Li 3 PS 4 ) 2 S n ), and -[S] n - containing polysulfides. ,− The more comprehensive descriptions on oxidative and reductive electrolyte degradation are summarized in refs and . In short, a kinetic electrochemical stability window for these electrolytes exists, and once the solid electrolytes are decomposed, their decomposition products become redox-active.…”

Section: Challengesmentioning

confidence: 99%

Toward Practical Solid-State Lithium–Sulfur Batteries: Challenges and Perspectives

Ohno

Zeier

2021

Acc. Mater. Res.

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Conspectus The energy density of the ubiquitous lithium-ion batteries is rapidly approaching its theoretical limit. To go beyond, a promising strategy is the replacement of conventional intercalation-type materials with conversion-type materials possessing substantially higher capacities. Among the conversion-type cathode materials, sulfur constitutes a cost-effective and earth-abundant element with a high theoretical capacity that has a potential to be game-changing, especially within an emerging solid-state battery configuration. Employment of nonflammable solid electrolytes that improves battery safety and boosts the energy density, as lithium metal anodes are also viable. The long-standing inherent problem of conventional lithium–sulfur batteries, arising from the reaction intermediates dissolved in liquid electrolytes, can be eliminated with inorganic solid ion conductors. In particular, the highly conducting and easily processable lithium-thiophosphates have successfully enabled the lab-scale solid-state lithium–sulfur cells to achieve close-to-theoretical capacities. For applications requiring safe, energy-dense, lightweight batteries, solid-state lithium–sulfur batteries are an ideal choice that could surpass conventional lithium-ion batteries. Nevertheless, there are challenges specific to practical solid-state lithium–sulfur batteries, beyond the typical challenges inherent to solid-state batteries in general. While the conversion reaction of sulfur realizes a large specific capacity, the associated significant total volume changes of the active material results in contact losses among the cathode components and, consequently, decreases reversible capacity. Additionally, the ionically and electronically insulating active material requires composite formation with solid electrolytes and electron-conductive additives to secure sufficient ion and electron supply at a triple-phase boundary. However, the compositing process itself makes the carrier transport pathways very tortuous and requires the balancing of carrier transport and optimization of the attainable energy density. Lastly, the requirement of a high interfacial area to establish sufficient triple-phase boundaries promotes the degradation of the solid electrolytes, and the formation of less-conductive interphases further deteriorates the transport in the composites. This Account focuses on the challenges associated with developing practical solid-state lithium–sulfur batteries and provides an overview over recently developed concepts to tackle these critical challenges: (1) Introduction of the conversion efficiency to enable quantitative assessments of the impact of chemo-mechanical failure. (2) For long-term cycling, the electrolyte degradation at the interface and the electrochemical activity of the formed interphases come into play. Practical stability tests with increased interfacial areas and subsequently altered reversal potentials can quantify the magnitude of the electrolyte degradation and confirm influences of reversible redox activity o...

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Lithium Argyrodite as Solid Electrolyte and Cathode Precursor for Solid‐State Batteries with Long Cycle Life

Cited by 65 publications

References 59 publications

Highly Stable Halide‐Electrolyte‐Based All‐Solid‐State Li–Se Batteries

Highly Stable Halide‐Electrolyte‐Based All‐Solid‐State Li–Se Batteries

Challenges, interface engineering, and processing strategies toward practical sulfide‐based all‐solid‐state lithium batteries

Toward Practical Solid-State Lithium–Sulfur Batteries: Challenges and Perspectives

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