[논문]전고체전지용 황화물 고체전해질 습식 합성기술 동향

하윤철

doi:10.5229/jkes.2022.25.3.95

[국내논문] 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.

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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.

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