Morphological Effect on Reaction Distribution Influenced by Binder Materials in Composite Electrodes for Sheet-type All-Solid-State Lithium-Ion Batteries with the Sulfide-based Solid Electrolyte

Chen, Kezheng; Shinjo, Sae; Sakuda, Atsushi; Yamamoto, Kentaro; Uchiyama, Tomoki; Kuratani, Kentaro; Takeuchi, Tomonari; Orikasa, Yuki; Hayashi, Akitoshi; Tatsumisago, Masahiro; Kimura, Yuta; Nakamura, Takashi; Amezawa, Koji; Uchimoto, Yoshiharu

doi:10.1021/acs.jpcc.8b09569

Cited by 58 publications

(53 citation statements)

References 22 publications

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“…As recently demonstrated by X-ray absorption spectroscopy imaging of SSB cells using slurrycoated cathodes, several electrode fractions of different SOC may be present during cycling. 26 As can be seen in Fig. 2, the 003 reflection of charged material exhibits asymmetric broadening (toward higher 2y values), especially for the LiNbO 3 -coated NCM622 after the second charge cycle, thus hinting at the presence of at least one additional CAM fraction.…”

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confidence: 80%

Indirect state-of-charge determination of all-solid-state battery cells by X-ray diffraction

et al. 2019

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confidence: 80%

Indirect state-of-charge determination of all-solid-state battery cells by X-ray diffraction

et al. 2019

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“…NBR has been the most popular binder for sulfide-based ASLBs, owing to its favorable mechanical attributes (i.e., good adhesion, rubbery property) and its solubility in sulfide-compatible solvents (e.g., xylene). [43][44][45][46][47][48][49] For the preparation of DPE-type binders, however, the use of more-polar solvents is necessary, as they can dissolve Li salts such as LiTFSI, but counteract the dissolution of NBR. This complication led us to develop a new slurry fabrication protocol employing cosolvents, in which two solvent molecules work in synergy for the dissolution of NBR and LiTFSI, while being benign toward the dissolution of sulfide SE Li 6 PS 5 Cl 0.5 Br 0.5 (LPSX).…”

Section: Introductionmentioning

confidence: 99%

Tailoring Slurries Using Cosolvents and Li Salt Targeting Practical All‐Solid‐State Batteries Employing Sulfide Solid Electrolytes

Kim

Jun

et al. 2021

Advanced Energy Materials

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classes of materials, including sulfides (e.g., Li 5.5 PS 4.5 Cl 1.5 : [14,15] ≈10 mS cm −1 ), oxides (e.g., Li 7 La 3 Zr 2 O 12 : [16] 0.5 mS cm −1 ), closo-borates (e.g., 0 . 7 L i ( C B 9 H 10 ) -0 . 3 L i ( C B 11 H 12 ) : [ 12,17] 6.7 mS cm −1 ), and halides (e.g., Li 3 YCl 6 : [18,19] 0.5 mS cm −1 , Li 2.25 Zr 0.75 Fe 0.25 Cl 6 : [20] 1 mS cm −1 ). Furthermore, consideration of multiple aspects, such as mechanical sinterability, cost, and lightness (e.g., Li 6 PS 5 Cl: [14] 1.86 g cm −3 , Li 7 La 3 Zr 2 O 12 : [21] 5.11 g cm −3 , Li 3 YCl 6 : [18] 2.43 g cm −3 ), indicates that sulfide materials are highly competitive. [14,22,23] To integrate SEs into large-scale ASLBs for mass production, sheet-type electrodes and SE films are required. [24][25][26][27][28][29][30][31][32][33] For this, it is necessary to use soft polymeric binders to avoid delamination and to supplement the brittleness of the inorganic components of the electrode active materials and SEs. [34][35][36] Moreover, stresses generated by volumetric strains in electrode active materials upon repeated cycling can be buffered by the polymeric binders. [34,36,37] However, the introduction of even a small amount of polymeric binder (e.g., 1-2 wt%) in composite electrodes severely degrades the electrochemical performance of ASLBs (e.g., as much as ≈30 mA h g −1 of capacity loss for LiNi 0.6 Co 0.2 Mn 0.2 O 2 electrodes), due to the disruption of interfacial Li + contact. [27,34,38] To address this issue, several approaches have been introduced. Yamamoto and coworkers reported that a binder-free sheet-type battery fabricated using thermally decomposable polymers of poly(propylene carbonate) provided good performance, [39] but at the expense of the mechanical properties of the battery. Moreover, it was shown that it is possible to use small amounts of binders via a dry process employing a fibrous polytetrafluoroethylene binder. [40,41] However, a wet-slurry process for ASLBs is still imperative, as it could take advantage of the already-developed manufacturing infrastructure for LIBs.Recently, our group reported the preparation of Li + conductive polymeric binders based on solvate ionic liquids (SILs), which are a solvent-salt complex of Li salt and glyme, such as Li(G3) TFSI (G3: triethylene glycol dimethyl ether, LiTFSI: lithium bis(trifluoromethanesulfonyl)imide). [34] The use of solvents with an intermediate polarity such as dibromomethane (DBM) for Polymeric binders that can undergo slurry fabrication and minimize the disruption of interfacial Li+ contact are imperative for sheet-type electrodes and solid electrolyte films in practical all-solid-state Li batteries (ASLBs). Although dry polymer electrolytes (DPEs) are a plausible alternative, their use is complicated by the severe reactivity of sulfide solid electrolytes and the need to dissolve Li salts. In this study, a new scalable fabrication protocol for a Li + -conductive DPE-type binder, nitrile-butadiene rubber (NBR)-LiTFSI, is reported. The less-polar dibromomethane and more-polar hexyl b...

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“…7,8,10 Especially, gaining insight into the reaction distribution in the composite is key to understanding its structure and electrochemical properties. While studies attempting to gain such insights using lithium-ion charge carrier batteries have been reported, the reaction distributions were widely analyzed indirectly based on the oxidation state changes of the active materials, 11,12 mainly due to the lack of suitable analytical techniques for this purpose. The available techniques for analyzing the light element lithium are mostly limited to scanning transmission electron microscopy combined with electron energy loss spectroscopy.…”

Section: Introductionmentioning

confidence: 99%

Ex-situ Analysis of Lithium Distribution in a Sulfide-based All-solid-state Lithium Battery by Particle-induced X-ray and Gamma-ray Emission Measurements

et al. 2020

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Lithium distribution in the composite electrode of an all-solid-state lithium battery was analyzed by microbeamparticle-induced X-ray emission and gamma-ray emission techniques. Two kinds of pellet-type cells, incorporating LiCoO 2 as the cathode-active material and the superionic conductor Li 10 GeP 2 S 12 as the solid electrolyte, were prepared: one in the as-prepared state and the other in the charged state. Changes in the lithium distribution near the interface of the composite cathode and separator were visualized by normalizing lithium/cobalt and lithium/ germanium intensity. Lithium extraction from LiCoO 2 due to charging was confirmed by the decrease in normalized intensity at the cathode composite region. The evaluation of the lithium concentration variation in the composite electrode for the all-solid-state battery during the electrochemical reactions could provide essential information for construction of a favorable composite electrode to enable preparing high-performance all-solid-state lithium batteries.

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Morphological Effect on Reaction Distribution Influenced by Binder Materials in Composite Electrodes for Sheet-type All-Solid-State Lithium-Ion Batteries with the Sulfide-based Solid Electrolyte

Cited by 58 publications

References 22 publications

Indirect state-of-charge determination of all-solid-state battery cells by X-ray diffraction

Indirect state-of-charge determination of all-solid-state battery cells by X-ray diffraction

Tailoring Slurries Using Cosolvents and Li Salt Targeting Practical All‐Solid‐State Batteries Employing Sulfide Solid Electrolytes

Ex-situ Analysis of Lithium Distribution in a Sulfide-based All-solid-state Lithium Battery by Particle-induced X-ray and Gamma-ray Emission Measurements

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