[논문]전고체전지용 황화물 고체전해질 습식 합성기술 동향

하윤철

doi:10.5229/jkes.2022.25.3.95

전고체전지용 황화물 고체전해질 습식 합성기술 동향
A Review on the Wet Chemical Synthesis of Sulfide Solid Electrolytes for All-Solid-State Li Batteries 원문보기

전기화학회지 = Journal of the Korean Electrochemical Society, v.25 no.3, 2022년, pp.95 - 104

초록
AI-Helper

상용 리튬이온전지의 에너지밀도 한계와 안전성 이슈로 불연성 전고체전지 개발이 현안이 되고 있다. 특히, 전기자동차를 위한 차세대 이차전지에 황화물 고체전해질의 적용 가능성이 높아지면서, 고체전해질의 대량생산과 저가격화를 위한 노력 또한 활발해 진행되고 있다. 황화물 고체전해질에 관한 현재까지의 대부분의 연구에서는 조성 및 불순물 제어가 용이하고 균질화와 열처리 시간을 줄일 수 있는 고에너지 기계적 밀링법을 이용하여 열역학적으로 안정한 상 및 준-안정한 상에 대한 탐색을 수행해 왔다. 이를 통해 액체 전해질의 리튬이온전도도를 능가하는 다양한 황화물 고체전해질이 보고되어, 고에너지밀도 고안전성 전고체전지 구현에 대한 기대가 커지고 있다. 그러나, 고에너지 기계적 밀링법은 대량생산에 따른 동일 물성 획득이 쉽지 않고, 입도나 형상 제어가 용이하지 않으며, 분쇄-분급 과정에서 물성의 열화가 발생하는 단점이 알려져 있다. 이에 비해 대량생산과 저가격화에 유리한 습식 합성기술은 아직 다양한 고체전해질 제조에 응용되지는 못하고 있다. 습식 합성기술에서는 입자형, 용액형, 또는 혼합형으로 전구체를 합성하고 용매를 제거한 후 열처리하는 공정을 통해 제조하고 있으나, 전구체의 형성 메커니즘에 대한 명확한 규명도 아직 이루어지지 않고 있다. 본 총설에서는 용매 내 원료들의 반응 메커니즘을 중심으로 한 황화물 고체전해질의 습식 합성기술 동향을 살펴보고자 한다.

Abstract ▼ AI-Helper

The development of non-flammable all-solid-state batteries (ASSLBs) has become a hot topic due to the known drawbacks of commercial lithium-ion batteries. As the possibility of applying sulfide solid electrolytes (SSEs) for electric vehicle batteries increases, efforts for the low-cost mass-production are actively underway. Until now, most studies have used high-energy mechanical milling, which is easy to control composition and impurities and can reduce the process time. Through this, various SSEs that exceed the Li+ conductivity of liquid electrolytes have been reported, and expectations for the realization of ASSLBs are growing. However, the high-energy mechanical milling method has disadvantages in obtaining the same physical properties when mass-produced, and in controlling the particle size or shape, so that physical properties deteriorate during the full process. On the other hand, wet chemical synthesis technology, which has advantages in mass production and low price, is still in the initial exploration stage. In this technology, SSEs are mainly manufactured through producing a particle-type, solution-type, or mixed-type precursor, but a clear understanding of the reaction mechanism hasn't been made yet. In this review, wet chemical synthesis technologies for SSEs are summarized regarding the reaction mechanism between the raw materials in the solvent.

주제어

표/그림 (8)

그림 Fig. 1. Schematic of wet chemical synthesis of sulfide solid electrolytes with three different types of intermediated precursors. Image adapted and modified from Ref. 21.
그림 Fig. 2. Overview of reactivities in the Li₂S-P₂S₅-(LiX) system in solution. The reaction types 1, 2 and 3 denote particle-type, solution-type and mixed-type, respectively. Image adapted and modified from Ref. 22.
표 Table 1. Summary of sulfide solid electrolytes produced by wet chemical synthesis
그림 Fig. 3. Particle-type wet chemical synthesis of β-Li₃PS₄ from Li₃PS₄·3THF precursors. (a) Morphology of as-synthesized Li₃PS₄·3THF particles. (b) Morphology of nanoporous β-Li3PS4 particles. (c) Surface of the nanoporous β-Li₃PS₄. (d) XRD patterns of as-synthesized Li₃PS₄·3THF, amorphous Li₃PS₄ prepared by heating Li₃PS₄·3THF at 80 °C, and nanoporous β-Li₃PS₄ prepared by heating Li₃PS₄·3THF at 140 °C. (e) Arrhenius plots for nanoporous β-Li₃PS₄ (line a), bulk β-Li₃PS₄ (line b), and bulk γ-Li₃PS₄ (line c). (f) Thermal analysis for the as-synthesized powder. The black line is the TGA curve at 10 °C/min under N₂. The red and blue lines are the first and second DSC cycles from room temperature to 350 °C. Images adapted and modified from Ref. 23.
그림 Fig. 4. Solution-type wet chemical synthesis of Li argyrodites from THF-ethanol solution. (a) A photographic image of the THF suspension of the Li3PS4 precursor. (b) A photographic image of the THF-ethanol precursor solution of Li₆PS₅Br. (c) Raman spectra of the THF-ethanol precursor solution of Li₆PS₅Br, LP-550 (liquid-phase method, heattreated at 550 °C), and MC-550 (mechanochemical method, heat-treated at 550 °C). (d) XRD patterns of LP-150 (liquidphase method, heat-treated at 150 °C), LP-550, and MC-550. (e) A schematic representation comparing wet chemical approaches vs. traditional ball-milling approaches. (f) XRD pattern and SEM image (inset) of LI₆PS₅Cl from solution synthesis. Images (a-d) and (e-f) adapted and modified from Ref. 33 and 34.
표 Table 2. Summary of the ionic and electronic conductivities of Li-argyrodites prepared through wet-chemical method³⁴⁾
그림 Fig. 5. Mixed-type wet chemical synthesis of Li₇P₃S₁₁ from ACN solution. (a) Photographs of material state during the synthesis procedure. (b) XRD patterns of the SSE-180 (heat-treated at 180 °C), SSE-220 (heat-treated at 220 °C), and Li₇P₃S₁₁ phase (ICDD#157564). (c) Impedance spectra of the pelletized SSE-180 (dotted green line: EIS data, continuous blue line: fitted data) and SSE-220 (dotted red line) samples. Images adapted and modified from Ref. 36.
그림 Fig. 6. Proposed reaction mechanism for solvent-mediated synthesis of Li₂S-P₂S₅ glass and glass-ceramic solid electrolytes. Images adapted and modified from Ref. 37.

참고문헌 (39)

M. S. Ziegler and J. E. Trancik, Re-examining rates of lithium-ion battery technology improvement and cost decline, Energy Environ. Sci., 14(4), 1635-1651 (2021).

상세보기
K. Liu, Y. Liu, D. Lin, A. Pei, and Y. Cui, Materials for lithium-ion battery safety, Sci. Adv., 4(6), eaas9820 (2018).

상세보기
A. Manthiram, X. Yu, and S. Wang, Lithium battery chemistries enabled by solid-state electrolytes, Nat. Rev. Mater., 2, 16103 (2017).

상세보기
N. Kamaya, K. Homma, Y. Yamakawa, M. Hirayama, R. Kanno, M. Yonemura, T. Kamiyama, Y. Kato, S. Hama, K. Kawamoto, and A. Mitsui, A lithium superionic conductor, Nat. Mater., 10, 682-686 (2011).

상세보기
Y. Seino, T. Ota, K. Takada, A. Hayashi, and M. Tatsumisago, A sulphide lithium super ion conductor is superior to liquid ion conductors for use in rechargeable batteries, Energy Environ. Sci., 7(2), 627-631 (2014).

상세보기
Y. Kato, S. Hori, T. Saito, K. Suzuki, M. Hirayama, A. Mitsui, M. Yonemura, H. Iba, and R. Kanno, High-power all-solid-state batteries using sulfide superionic conductors, Nat. Energy, 1, 16030 (2016).
H.-J. Deiseroth, S.-T. Kong, M. Schlosser, and C. Reiner, Lithium argyrodite, WO Patent WO/2009/047254 (2009).
K. Terai, F. Utsuno, T. Umeki, M. Nakagawa, and H. Yamaguchi, Sulfide solid electrolyte, WO Patent WO/2018/047565 (2018).
T. Tsukasa, C. Takashi, and I. Takahiro, Sulfide-based solid electrolyte particles, WO Patent WO/2019/176895 (2019).
C. Yu, Y. Li, M. Willans, Y. Zhao, K. R. Adair, F. Zhao, W. Li, S. Deng, J. Liang, M. N. Banis, R. Li, H. Huang, L. Zhang, R. Yang, S. Lu, Y. Huang, and X. Sun, Superionic conductivity in lithium argyrodite solid-state electrolyte by controlled Cl-doping, Nano Energy, 69, 104396 (2020).

상세보기
P. Adeli, J. D. Bazak, K. H. Park, I. Kochetkov, A. Huq, G. R. Goward, and L. F. Nazar, Boosting solid-state diffusivity and conductivity in lithium superionic argyrodites by halide substitution, Angew. Chem. Int. Ed., 58(26), 8681-8686 (2019).
W. D. Jung, J.-S. Kim, S. Choi, S. Kim, M. Jeon, H.-G. Jung, K. Y. Chung, J.-H. Lee, B.-K. Kim, J.-H. Lee, and H. Kim, Superionic halogen-rich Li-argyrodites using in situ nanocrystal nucleation and rapid crystal growth, Nano Lett., 20(4), 2303-2309 (2020).

상세보기
X. Feng, P.-H. Chien, Y. Wang, S. Patel, P. Wang, H. Liu, M. Immediato-Scuotto, and Y.-Y. Hu, Enhanced ion conduction by enforcing structural disorder in Li-deficient argyrodites Li 6-x PS 5-x Cl 1+x , Energy Storage Mater., 30, 67-73 (2020).
K. Oh, D. Chang, B. Lee, D.-H. Kim, G. Yoon, I. Park, B. Kim, and K. Kang, Native defects in Li 10 GeP 2 S 12 and their effect on lithium diffusion, Chem. Mater., 30(15), 4995-5004 (2018).
M. A. Kraft, S. Ohno, T. Zinkevich, R. Koerver, S. P. Culver, T. Fuchs, A. Senyshyn, S. Indris, B. J. Morgan, and W. G. Zeier, Inducing high ionic conductivity in the lithium superionic argyrodites Li 6+x P 1-x Ge x S 5 I for all-solid-state batteries, J. Am. Chem. Soc., 140(47), 16330-16339 (2018).
L. Zhou, A. Assoud, Q. Zhang, X. Wu, and L. F. Nazar, New family of argyrodite thioantimonate lithium superionic conductors, J. Am. Chem. Soc., 141(48), 19002-19013 (2019).

상세보기
Y. Lee, J. Jeong, D.-H. Lim, S.-O. Kim, H.-G. Jung, K. Y. Chung, and S. Yu, Superionic Si-substituted lithium argyrodite sulfide electrolyte Li 6+x Sb 1-x Si x S 5 I for all-solid-state batteries, ACS Sustain. Chem. Eng., 9(1), 120-128 (2021).
Y. Lee, J. Jeong, H. J. Lee, M. Kim, D. Han, H. Kim, J. M. Yuk, K.-W. Nan, K. Y. Chung, H.-G. Jung, and S. Yu, Lithium argyrodite sulfide electrolytes with high ionic conductivity and air stability for all-solid-state Li-Ion batteries, ACS Energy Lett., 7(1), 171-179 (2022).
A. Banik, T. Famprikis, M. Chidiu, S. Ohno, M. A. Kraft, and W. G. Zeier, On the underestimated influence of synthetic conditions in solid ionic conductors, Chem. Sci., 12, 6238-6263 (2021).

상세보기
Y.-C. Ha, S.-M. Lee, B. G. Kim, G. Park, J.-W. Park, J. Park, J.-H. Yu, W.-J. Lee, Y.-J. Lee, and H. Choi, Method for producing solid electrolyte, solid electrolyte prepared therefrom, and all-solid battery comprising the same, WO Patent PCT/KR2022/000464 (2022).
A. Miura, N. C. Rosero-Navarro, A. Sakuda, K. Tadanaga, N. H. H. Phuc, A. Matsuda, N. Machida, A. Hayashi, and M. Tatsumisago, Liquid-phase syntheses of sulfide electrolytes for all-solid-state lithium battery, Nat. Rev. Chem., 3, 189-198 (2019).

상세보기
M. Ghidiu, J. Ruhl, S. P. Culver, and W. G. Zeier, Solution-based synthesis of lithium thiophosphate superionic conductors for solid-state batteries: a chemistry perspective, J. Mater. Chem. A, 7, 17735-17753 (2019).

상세보기
Z. Liu, W. Fu, E. A. Payzant, X. Yu, Z. Wu, N. J. Dudney, J. Kiggans, K. Hong, A. J. Rondinone, and C. Liang, Anomalous high ionic conductivity of nanoporous β-Li 3 PS 4 , J. Am. Chem. Soc., 135(3), 975-978 (2013).
K. Homma, M. Yonemura, T. Kobayashi, M. Nagao, M. Hirayama, and R. Kanno, Crystal structure and phase transitions of the lithium ionic conductor Li 3 PS 4 , Solid State Ion., 182(1), 53-58 (2011).
M. Calpa, H. Nakajima, S. Mori, Y. Goto, Y. Mizuguchi, C. Moriyoshi, Y. Kuroiwa, N. C. Rosero-Navarro, A. Miura, and K. Tadanaga, Formation mechanism of β-Li 3 PS 4 through decomposition of complexes, Inorg. Chem., 60(10), 6964-6970 (2021).
F. Marchini, B. Porcheron, G. Rousse, L. A. Blanquer, L. Droguet, D. Foix, T. Koc, M. Deschamps, and J. M. Tarascon, The hidden side of nanoporous β-Li 3 PS 4 solid electrolyte, Adv. Energy Mater., 11(34), 2101111 (2021).
E. Rangasamy, Z. Liu, M. Gobet, K. Pilar, G. Sahu, W. Zhou, H. Wu, S. Greenbaum, and C. Liang, An iodide-based Li 7 P 2 S 8 I superionic conductor, J. Am. Chem. Soc., 137(4), 1384-1387 (2015).
S. J. Sedlmaier, S. Indris, C. Dietrich, M. Yavuz, C. Drager, F. von Seggern, H. Sommer, and J. Janek, Li 4 PS 4 I: A Li + superionic conductor synthesized by a solvent-based soft chemistry approach, Chem. Mater., 29(4), 1830-1835 (2017).
S.-J. Choi, S.-H. Lee, Y.-C. Ha, J.-H. Yu, C.-H. Doh, Y. Lee, J.-W. Park, S.-M. Lee, and H.-C. Shin, Synthesis and electrochemical characterization of a glass-ceramic Li 7 P 2 S 8 I solid electrolyte for all-solid-state Li-ion batteries, J. Electrochem. Soc., 165, A957-A962 (2018).
S.-J. Choi, S.-H. Choi, A. D. Bui, Y.-J. Lee, S.-M. Lee, H.-C. Shin, and Y.-C. Ha, LiI-doped sulfide solid electrolyte: enabling a high-capacity slurry-cast electrode by low-temperature post-sintering for practical all-solid-state lithium batteries, ACS Appl. Mater. Interfaces, 10(37), 31404-31412 (2018).

상세보기
A. D. Bui, S.-H. Choi, H. Choi, Y.-J. Lee, C.-H. Doh, J.-W. Park, B. G. Kim, W.-J. Lee, S.-M. Lee, and Y.-C. Ha, Origin of the outstanding performance of dual halide doped Li 7 P 2 S 8 X (X I, Br) solid electrolytes for all-solid-state lithium batteries, ACS Appl. Energy Mater., 4(1), 1-8 (2021).
S. Yubuchi, A. Hayashi, and M. Tatsumisago, Application to all-solid-state batteries with Li 6 PS 5 Br electrolyte prepared by a liquid-phase technique, Meet. Abstr., MA2016-02, 3982 (2016).
S. Yubuchi, M. Uematsu, C. Hotehama, A. Sakuda, A. Hayashi, and M. Tatsumisago, An argyrodite sulfide-based superionic conductor synthesized by a liquid-phase technique with tetrahydrofuran and ethanol, J. Mater. Chem. A, 7, 558-566 (2019).

상세보기
L. Zhou, K.-H. Park, X. Sun, F. Lalere, T. Adermann, P. Hartmann, and L. F. Nazar, Solvent-engineered design of argyrodite Li 6 PS 5 X (X Cl, Br, I) solid electrolytes with high ionic conductivity, ACS Energy Lett., 4(1), 265-270 (2019).
M.-J. Kim, I.-H. Choi, S. C. Jo, B. G. Kim, Y.-C. Ha, S.-M. Lee, S. Kang, K.-J. Baeg, and J.-W. Park, A novel strategy to overcome the hurdle for commercial all-solid-state batteries via low-cost synthesis of sulfide solid electrolytes, Small Methods, 5(11), 2100793 (2021).

상세보기
M. Calpa, N. C. Rosero-Navarro, A. Miura, and K. Tadanaga, Instantaneous preparation of high lithium-ion conducting sulfide solid electrolyte Li 7 P 3 S 11 by a liquid phase process, RSC Adv., 7, 46499-46504 (2017).
F. M. Delnick, G. Yang, E. C. Self, H. M. Meyer III, and J. Nanda, Investigation of complex intermediates in solvent-mediated synthesis of thiophosphate solid-state electrolytes, J. Phys. Chem. C, 124(50), 27396-27402 (2020).

상세보기
K. Yamamoto, M. Takahashi, K. Ohara, N. H. H. Phuc, S. Yang, T. Watanabe, T. Uchiyama, A. Sakuda, A. Hayashi, M. Tatsumisago, H. Muto, A. Matsuda, and Y. Uchimoto, Synthesis of sulfide solid electrolytes through the liquid phase: optimization of the preparation conditions, ACS Omega, 5(40), 26287-26294 (2020).

상세보기
M. Calpa, N. C. Rosero-Navarro, A. Miura, K. Terai, F. Utsuno, and K. Tadanaga, Formation mechanism of thiophosphate anions in the liquid-phase synthesis of sulfide solid electrolytes using polar aprotic solvents, Chem. Mater., 32(22), 9627-9632 (2020).

상세보기

저자의 다른 논문 :

표제어: PCR

동의어: Packet Collision Rate

용어 설명 출처 목록 (6)

용어 설명: PCR은 세균 특이성이 있는 primer를 이용하여 적은 수의 세균이 있을지라도 쉽게 검출할 수 있는 유용한 방법이며, 이를 이용하여 구강 내 치면세균막이나 타액에서 직접 세균을 검출할 수 있게 되었다[8].

내보내기 구분	파일저장 인쇄 메일전송
구성항목	기본정보 상세정보 관리번호, 논문명, 저널/프로시딩명, 저자 , 발행년, 권, 호, 시작페이지, 끝페이지, 발행기관 관리번호, 논문명, 대등논문명, 저자 , 저널/프로시딩명, 발행기관, 발행년, 발행언어, 권, 호, 시작페이지, 끝페이지, ISBN, ISSN, 주제분야, 키워드, 초록(한글), 초록(영문), 저자(소속기관)
저장형식	Text(ASCII format) Excel format RefWorks Direct Export RIS format (for Reference Manager, ProCite, EndNote), Scholar's Aids, Mendeley
메일정보	받는사람 (필수) @ 보내는사람 (선택) @ 제목 내용 KISTI 검색결과 이메일 서비스
안내	총 건의 자료가 검색되었습니다. 다운받으실 자료의 인덱스를 입력하세요. (1-10,000) 검색결과의 순서대로 최대 10,000건 까지 다운로드가 가능합니다. 데이타가 많을 경우 속도가 느려질 수 있습니다.(최대 2~3분 소요) 다운로드 파일은 UTF-8 형태로 저장됩니다. 파일의 내용이 제대로 보이지 않을실 때는 웹브라우저 상단의 보기 -> 인코딩 -> 자동선택 여부를 확인하십시오. ~ Text(ASCII format) Excel format

연합인증