Operando EDXRD Study of All‐Solid‐State Lithium Batteries Coupling Thioantimonate Superionic Conductors with Metal Sulfide

Sun, Xiao; Stavola, Alyssa M.; Cao, Daxian; Bruck, Andrea M.; Wang, Ying; Zhang, Yunlu; Luan, Pengcheng; Gallaway, Joshua W.; Zhu, Hongli

doi:10.1002/aenm.202002861

Cited by 36 publications

(36 citation statements)

References 38 publications

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cathode materials into ASSBs could further increase the specific energy substantially. [11] However, the morphological, structural, and chemical changes during cycling are highly complex [12] and the cycling performance of ASSBs at room temperature (RT) with conversion-type cathode materials, such as S, FeS 2 , or Li 2 S, is not yet satisfactory. [13][14][15] Whereas liquid electrolyte can easily infiltrate the porous cathode composite to homogeneously contact active material particles and form a fast ion transport network, this is more difficult to achieve in ASSBs.

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confidence: 99%

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

Wang

Tang

Zhang

et al. 2021

Advanced Energy Materials

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All‐solid‐state batteries with conversion‐type cathodes promise to exceed the performance of lithium‐ion batteries due to their high theoretical specific energy and potential safety. However, the reported performance of solid‐state batteries is still unsatisfactory due to poor electronic and ionic conduction in the composite cathodes. Here, in situ formation of active material as well as highly effective ion‐ and electron‐conducting paths via electrochemical decomposition of Li6PS5Cl0.5Br0.5 (LPSCB)/multiwalled carbon nanotube mixtures during cycling is reported. Effectively, the LPSCB electrolyte forms a multiphase conversion‐type cathode by partial decomposition during the first discharge. Comprehensive characterization, especially operando pressure monitoring, reveals a co‐redox process of two redox‐active elements during cycling. The monolithic LPSCB‐based cell shows stable cycling over 1000 cycles with a very high capacity retention of 94% at high current density (0.885 mA cm−2, ≈0.7 C) at room temperature and a high areal capacity of 12.56 mAh cm−2 is achieved.

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confidence: 99%

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

Wang

Tang

Zhang

et al. 2021

Advanced Energy Materials

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“…In recent years, various SEs have been synthesized with much-improved moisture stability, e.g., As-substituted Li 4 SnS 4 , [6] Sb-doped Li 10 GeP 2 S 12 , [7] and Li 6.6 Ge 0.6 Sb 0.4 S 5 I. [8] To fully realize the high energy density of ASSLBs, thin lithium metal is preferred, but lithium dendrite growth through the SE separator and SE reduction by Li metal needs to be addressed.…”

mentioning

confidence: 99%

Deciphering Interfacial Chemical and Electrochemical Reactions of Sulfide‐Based All‐Solid‐State Batteries

Wang

Hwang

Jiang

et al. 2021

Advanced Energy Materials

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The success of ASSLBs could eventually eliminate the mileage anxiety and safety concerns of electric vehicles (EVs). To enable ASSLBs, various solid-state electrolytes have been intensively developed over the past decades, such as sulfide electrolytes (SEs), [1b,c,2] oxide electrolytes, [3] polymer-based electrolytes, [4] and emerging solid-state halide electrolytes (Li 3 MCl 6 , M = Y, In, Er, Sc, etc.). [5] Owing to the high ionic conductivity and soft mechanical properties of SEs, it is widely believed that SE-based ASSLBs will be a leading contender for large-scale energy storage, particularly for the fast-growing industry of electric vehicles.However, several challenges hinder the development of SE-based ASSLBs, including (1) moisture sensitivity and narrow electrochemical windows of SEs;(2) large interfacial resistance between electrodes and SEs that is caused by detrimental interfacial reactions; and (3) shortcircuits when lithium dendrites penetrate through thin SE separators. In recent years, various SEs have been synthesized with much-improved moisture stability, e.g., As-substituted Li 4 SnS 4 , [6] Sb-doped Li 10 GeP 2 S 12 , [7] and Li 6.6 Ge 0.6 Sb 0.4 S 5 I. [8] To fully realize the high energy density of ASSLBs, thin lithium metal is preferred, but lithium dendrite growth through the SE separator and SE reduction by Li metal needs to be addressed. Large interfacial resistance resulting from interfacial reactions is widely acknowledged as one of the main challenges in sulfide electrolytes (SEs)-based all-solid-state lithium batteries (ASSLBs). However, the root cause of the large interfacial resistance between the SEs and typical layered oxide cathodes is not fully understood yet. Here, it is shown that interfacial oxygen loss from single-crystal LiNi 0.5 Mn 0.3 Co 0.2 O 2 (SC-NMC532) chemically oxidizes Li 10 GeP 2 S 12 , generating oxygen-containing interfacial species. Meanwhile, the interfacial oxygen loss also induces a structural change of oxide cathodes (layered-to-rock salt). In addition, the high operation voltage can electrochemically oxidize SEs to form non-oxygen species (e.g., polysulfides). These chemically and electrochemically oxidized species, together with the interfacial structural change, are responsible for the large interfacial resistance at the cathode interface. More importantly, the widely adopted interfacial coating strategy is effective in suppressing chemically oxidized oxygencontaining species and mitigating the coincident interfacial structural change but is unable to prevent electrochemically induced non-oxygen species. These findings provide a deeper insight into the large interfacial resistance between the typical SE and layered oxide cathodes, which may be of assistance for the rational interface design of SE-based ASSLBs in the future.

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“…Synchrotron‐based XRD (SXRD), for example, energy‐disperse XRD (EDXRD), can provide high spatial resolution (spot size in micrometers), so that it can detect the interface products by scanning across the customized cell. [ 98 ] Furthermore, the high time resolution (data acquisition in seconds) derived from the high photon flux of SR benefits to observe instantaneous interfacial evolutions with operando setups [69b,99] . Operando SXRD was always coupled with XT to provide phase analysis and images simultaneously with the nondestructive feature, as displayed in Figure a.…”

Section: Characterizations For Electrode/sulfide Interfacesmentioning

confidence: 99%

“…Zhu and co‐workers reported using SXRD to identify each component in one operating cell (Figure 16b) and then analyzed the stability of Li 6.6 Ge 0.6 Sb 0.4 S 5 I SEs during charging and discharging. [ 99 ] Very recently, Bruce et al observed the cracking and its correlation to the growth of Li dendrites within a symmetric cell (Li/Li 6 PS 5 Cl/Li) via using combined operando SXRD and XT techniques. The SXRD mapping in one 4 × 4 Mm 2 area of the Li anode clearly indicated the location and intensity of Li dendrites that were recognized by the diffraction peak of Li (110) lattice plane (Figure 16c).…”

Section: Characterizations For Electrode/sulfide Interfacesmentioning

confidence: 99%

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Emerging Characterization Techniques for Electrode Interfaces in Sulfide‐Based All‐Solid‐State Lithium Batteries

Zhao

Zhang

et al. 2021

Small Structures

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All‐solid‐state Li batteries (ASSLBs) are attracting increasing attentions due to their improved safety and high energy density compared with conventional liquid electrolyte‐based Li‐ion batteries (LIBs). ASSLBs based on sulfide solid‐state electrolytes (SEs) is one of the most popular categories, because sulfide SEs have a very competitive ionic conductivity (up to over 10−2 S cm−1 at room temperature), medium mechanical stiffness, decent contact with electrode materials, and negligible grain boundary resistance. However, interface problems between electrode materials and sulfide SEs seriously plague the development of high‐performance sulfide‐based ASSLBs. In‐depth understandings on the electrode interface problems are pivotal to propose and explore effective strategies to alleviate those issues. In recent years, diverse advanced characterization techniques have been developed, which deepen insights into the problematic interface from physical, chemical, electrochemical, and mechanochemical perspectives. Herein, electrode interfaces and their fundamental knowledge in sulfide‐based ASSLBs are first clarified. Second, various emerging characterizations are overviewed to illustrate the interfacial issues on both oxide cathode/sulfide SE and Li anode/sulfide SE interfaces. Meanwhile, advantages and disadvantages of each characterization techniques are explicated. Finally, an outlook of advanced characterizations that are specifically adapted for interface analysis in sulfide‐based ASSLBs is proposed.

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Operando EDXRD Study of All‐Solid‐State Lithium Batteries Coupling Thioantimonate Superionic Conductors with Metal Sulfide

Cited by 36 publications

References 38 publications

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

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

Deciphering Interfacial Chemical and Electrochemical Reactions of Sulfide‐Based All‐Solid‐State Batteries

Emerging Characterization Techniques for Electrode Interfaces in Sulfide‐Based All‐Solid‐State Lithium Batteries

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