1. Home
  2. Honda R&D Technical Review Vol.33 N...
  3. Comprehensive Study of Solvents for...

Technical Review e-Book: Summary

Comprehensive Study of Solvents for Wet Process Applied to Sulfide-based All Solid State Battery

Article of Honda R&D Technical Review Vol.33 No.2


In the process of creating a wet process for a sulfide-based all solid state battery, it was necessary to search for suitable solvents. A systematic examination was therefore made of solid electrolytes and the reactivity of solvents. A halogen-doped argyrodite solid electrolyte that shows high lithium-ionic conductivity did not react with a hydrocarbon compound containing no polar group. With ethers, esters, ketones, and nitriles, however, the oxygen atoms and nitrogen atoms in their respective polar groups interact strongly with the solid electrolyte and were expected to form complexes with the lithium ions in the electrolyte. However, solvents having an alkyl chain length with a carbon number of four were not found to form complexes and the ionic conductivity of the solid electrolyte had not been markedly diminished. This is thought to occur because the increase in length of alkyl chains decreases the surface area accessible to coordinating oxygen atoms in the solvent molecules, thereby inhibiting the approach of the solvent to the surface of the solid electrolyte. Setting the carbon number of four or greater for the alkyl group chain length as a solvent search index yielded a direction to pursue for practical application of a wet process.


(1) (a) Armand, M., Tarascon, J.-M.: Building better batteries, Nature, Vol. 451, p. 652-657, (2008); (b) Balali, Y., Stegen. S.: Review of energy storage systems for vehicles based on technology, environmental impacts, and costs, Renewable and Sustainable Energy Reviews, Vol. 135, Article 110185, (2021)
(2) https://www.nedo.go.jp/content/100919683.pdf
(3) Kato, Y., Hori, S., Kanno, R.: Li10GeP2S12-Type Superionic Conductors: Synthesis, Structure, and Ionic Transportation, Advanced energy materials, Vol. 10, Issue 42, p. 2002153, (2020)
(4) Kamaya, N., Homma, K., Yamakawa, Y., Hirayama, M., Kanno, R., Yonemura, M., Kamiyama, T., Kato, Y., Hama, S., Kawamoto, K., Mitsui, A.: A lithium superionic conductor, Nature Materials, Vol. 10, p. 682-686, (2011)
(5) Kato, Y., Hori, S., Saito, T., Suzuki, K., Hirayama, M., Mitsui, A., Yonemura, M., Iba, H., Kanno, R.: High-power all-solid-state batteries using sulfide superionic conductors, Nature Energy, Vol. 1, p. 1-7, (2016)
(6) Zhang, Q., Cao, D., Ma, Y., Natan, A., Aurora, P., Zhu, H.: Sulfide-Based Solid-State Electrolytes: Synthesis, Stability, and Potential for All-Solid-State Batteries, Advanced Materials, Vol. 31, Issue 44, p. 1901131, (2019)
(7) Zheng, Y., Yao, Y., Ou, J., Li, M., Luo, D., Dou, H., Li, Z., Amine, K., Yu, A., Chen, Z.: A review of composite solid-state electrolytes for lithium batteries: fundamentals, key materials and advanced structures, Chemical Society Reviews, Vol. 49, Issue 23, p. 8790-8839, (2020)
(8) Yamamoto, M., Terauchi, Y., Sakuda, A., Takahashi, M.: Binder-free sheet-type all-solid-state batteries with enhanced rate capabilities and high energy densities, Scientific Reports, Vol. 8, Article number 1212, (2018)
(9) Riphaus, N., Strobl, P., Stiaszny, B., Zinkevich, T., Yavuz, M., Schnell, J., Indris, S., Gasteiger, H. A., Sedlmaier, S. J.: Slurry-Based Processing of Solid Electrolytes: A Comparative Binder Study, Journal of The Electrochemical Society, Vol. 165, No. 16, A3993-A3999, (2018)
(10) Lee, K., Kim, S., Park, J., Park, S. H., Coskun, A., Jung, D. S., Cho, W., Choi, J. W.: Selection of Binder and Solvent for Solution-Processed All-Solid-State Battery, Journal of The Electrochemical Society, Vol. 164, No. 9, A2075-A2081, (2017)
(11) Chen, K., Shinjo, S., Sakuda, A., Yamamoto, K., Uchiyama, T., Kuratani, K., Takeuchi, T., Orikasa, Y., Hayashi, A., Tatsumisago, M., Kimura, Y., Nakamura, T., Amezawa, K., Uchimoto, Y.: 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, The Journal of Physical Chemistry C, Vol. 123, Issue 6, p. 3292-3298, (2019)
(12) Oh, D. Y., Nam, Y. J., Park, K. H., Jung, S. H., Cho S.-J., Kim, Y. K., Lee, Y.-G., Lee, S.-Y., Jung, Y. S.: Excellent Compatibility of Solvate Ionic Liquids with Sulfide Solid Electrolytes: Toward Favorable Ionic Contacts in Bulk-Type All-Solid-State Lithium-Ion Batteries, Advanced Energy Materials, Vol. 5, Issue 22, p. 1500865, (2015)
(13) Nam, Y. J., Cho, S.-J., Oh, D. Y., Lim, J.-M., Kim, S. Y., Song, J. H., Lee, Y.-G., Lee, S.-Y., Jung, Y. S.: Bendable and Thin Sulfide Solid Electrolyte Film: A New Electrolyte Opportunity for Free-Standing and Stackable High-Energy All-Solid-State Lithium-Ion Batteries, Nano Letters, Vol. 15, Issue 5, p. 3317-3323, (2015)
(14) Riphaus, N., Stiaszny, B., Beyer, H., Indris, S., Gasteiger, H. A., Sedlmaier, S. J.: Understanding Chemical Stability Issues between Different Solid Electrolytes in All-Solid-State Batteries, Journal of The Electrochemical Society, Vol. 166, No. 6, A975-A983, (2019)
(15) Yubuchi, S., Uematsu, M., Hotehama, C., Sakuda, A., Hayashi, A., Tatsumisago, M.: An argyrodite sulfide-based superionic conductor synthesized by a liquid-phase technique with tetrahydrofuran and ethanol, J. Mater. Chem. A, Vol. 7, p. 558-566, (2019)
(16) Yubuchi, S., Uematsu, M., Deguchi, M., Hayashi, A., Tatsumisago, M.: Lithium-Ion-Conducting Argyrodite-Type Li6PS5X (X = Cl, Br, I) Solid Electrolytes Prepared by a Liquid-Phase Technique Using Ethanol as a Solvent, ACS Applied Energy materials, Vol. 1, Issue 8, p. 3622-3629, (2018)
(17) Phuc, N. H. H., Totani, M., Morikawa, K., Muto, H., Matsuda, A.: Preparation of Li3PS4 solid electrolyte using ethyl acetate as synthetic medium, Solid State Ionics, Vol. 288, p. 240-243, (2016)
(18) Barrow, G. M.: Physical chemistry, International student edition, 7th printing, Chapter 21, Surface and heterogeneous catalysis, p. 731-754, (1983)
(19) Fujimoto, K.: Kinetic Studies on Mineral Dissolution into Aqueous Solution: Reaction at Solid/Water Interface and Mass Transport, Journal of the Mineralogical Society of Japan, Vol. 24, No. 3, p. 159-168, (1995) (in Japanese)
(20) Whitesides, G. M., Laibinis, P. E.: Wet chemical approaches to the characterization of organic surfaces: self-assembled monolayers, wetting, and the physical-organic chemistry of the solid-liquid interface, Langmuir, Vol. 6, Issue 1, p. 87-96, (1990)
(21) Barthel, J., Buchner, R., Wismeth, E.: FTIR Spectroscopy of Ion Solvation of LiClO4 and LiSCN in Acetonitrile, Benzonitrile, and Propylene Carbonate, Journal of Solution Chemistry, Vol. 29, No. 10, p. 937-954, (2000)
(22) Seneviratne, V., Frech, R., Furneaux, J. E., Khan, M.: Characterization of Crystalline and Solution Phases of Diglyme-LiSbF6, The Journal of Physical Chemistry B, Vol. 108, No. 24, p. 8124-8128, (2004)
(23) Delley, B.: An all-electron numerical method for solving the local density functional for polyatomic molecules, The Journal of Chemical Physics, Vol. 92, Issue 1, p. 508-517, (1990)
(24) Delley, B.: From molecules to solids with the DMol3 approach, The Journal of Chemical Physics, Vol. 113, Issue 18, p. 7756-7764, (2000)
(25) Connolly, M. L.: Analytical molecular surface calculation, Journal of Applied Crystallography, Vol. 16, Issue 5, p. 548-558, (1983)
(26) Nakayama, J.: The Infra-red Absorption Spectra of Organophosphorus Compounds, Journal of Synthetic Organic Chemistry, Japan, Vol. 28, No. 2, p. 132-143, (1970) (in Japanese)
(27) Arai, Y., Yasue, T.: Introduction to Experimental Solid State Chemistry (XI), 7 Infrared Absorption Spectroscopy (2), Gypsum & Lime, No. 188, p. 47-60, (1984) (in Japanese)
(28) Olsher, U., Izatt, R. M., Bradshaw, J. S., Dalley, N. K.: Coordination Chemistry of Lithium Ion: A Crystal and Molecular Structure Review, Chemical Reviews, Vol. 91, Issue 2, p. 137-164, (1991)
(29) Zhou, L., Park, K.-H., Sun, X., Lalère, F., Adermann, T., Hartmann, P., Nazar, L. F.: Solvent-Engineered Design of Argyrodite Li6PS5X (X = Cl, Br, I) Solid Electrolytes with High Ionic Conductivity, ACS Energy Letters, Vol. 4, Issue 1, p. 265-270, (2019)
(30) Wang, Z., Jiang, Y., Wu, J., Jiang, Y., Huang, S., Zhao, B., Chen, Z., Zhang, J.: Reaction mechanism of Li2S-P2S5 system in acetonitrile based on wet chemical synthesis of Li7P3S11 solid electrolyte, Chemical Engineering Journal, Vol. 393, Article 124706, (2020)
(31) Wang, Y., Lu, D., Bowden, M., El Khoury, P. Z., Han, K. S., Deng, Z. D., Xiao, J., Zhang, J.-G., Liu, J.: Mechanism of Formation of Li7P3S11 Solid Electrolytes through Liquid Phase Synthesis, Chemistry of Materials, Vol. 30, Issue 3, p. 990-997, (2018)
(32) Qian, P., Matsuda, M., Miyashita, T.: Chiral molecular recognition in polymer Langmuir-Blodgett films containing axially chiral binaphthyl groups, Journal of the American Chemical Society, Vol. 115, Issue 13, p. 5624-5628, (1993)
(33) Qian, P., Nanjo, H., Yokoyama, T., Suzuki, T. M., Akasaka, K., Ohrui, H.: Chiral molecular patterns of self-assembled ion pairs composed of (R, S), (S)-16-methyloctadecanoic acid and 4,4′-bipyridine, Chemical Communications, Vol. 20, p. 2021-2022, (2000)
(34) Mahajan, Y. S., Kamath, R. S., Kumbhar, P. S., Mahajani, S. M.: Self-Condensation of Cyclohexanone over Ion Exchange Resin Catalysts: Kinetics and Selectivity Aspects, Industrial & Engineering Chemistry Research, Vol. 47, Issue 1, p. 25-33, (2008)
(35) Iwata, M., Emoto, S.: Aldol Condensation of Aldehydes with Ketones Promoted by the Copper(II) Ion. Orientation to the Chemical Model for Metalloaldolases, Bulletin of the Chemical Society of Japan, Vol. 49, No. 5, p. 1369-1374, (1976)

Author (organization or company)

Pu QIAN(Innovative Research Excellence)、Hiroshi SAKAI(Innovative Research Excellence)、Atsushi OGAWA(Innovative Research Excellence)、Hiroto MAEYAMA(Innovative Research Excellence)、Terumi FURUTA(Innovative Research Excellence)

We would like to get your opinion on this research paper. (This is only applicable to registered members.)