• 한국분말재료학회지
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• 제23권5호
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• pp.379-383
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• 2016

A thick film of $Li_7La_3Zr_2O_{12}$ (LLZO) solid-state electrolyte is fabricated using the tape casting process and is compared to a bulk specimen in terms of the density, microstructure, and ion conductivity. The final thickness of LLZO film after sintering is $240{\mu}m$ which is stacked up with four sheets of LLZO green films including polymeric binders. The relative density of the LLZO film is 83%, which is almost the same as that of the bulk specimen. The ion conductivity of a LLZO thick film is $2.81{\times}10^{-4}S/cm$, which is also similar to that of the bulk specimen, $2.54{\times}10^{-4}S/cm$. However, the microstructure shows a large difference in the grain size between the thick film and the bulk specimen. Although the grain boundary area is different between the thick film and the bulk specimen, the fact that both the ion conductivities are very similar means that no secondary phase exists at the grain boundary, which is thought to originate from nonstoichiometry or contamination.

• 한국재료학회지
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• 제31권11호
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• pp.614-618
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• 2021

As the size of market for electric vehicles and energy storage systems grows, the demand for lithium-ion batteries (LIBs) is increasing. Currently, commercial LIBs are fabricated with liquid electrolytes, which have some safety issues such as low chemical stability, which can cause ignition of fire. As a substitute for liquid electrolytes, solid electrolytes are now being extensively studied. However, solid electrolytes have disadvantages of low ionic conductivity and high resistance at interface between electrode and electrolyte. In this study, Li₇La₃Zr₂O₁₂ (LLZO), one of the best ion conducting materials among oxide based solid electrolytes, is fabricated through RF-sputtering and various electrochemical properties are analyzed. Moreover, the electrochemical properties of LLZO are found to significantly improve with co-sputtered Li₂O. An all-solid thin film battery is fabricated by introducing a thin film solid electrolyte and an Li₄Ti₅O₁₂ (LTO) cathode; resulting electrochemical properties are also analyzed. The LLZO/Li₂O (60W) sample shows a very good performance in ionic conductivity of 7.3×10^-8 S/cm, with improvement in c-rate and stable cycle performance.

• 전기화학회지
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• 제21권4호
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• pp.80-87
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• 2018

웨어러블 디바이스, 전기자동차와 에너지저장시스템에 대한 전력 수요가 증가함에 따라 리튬이온 전지에 있어서 안전성은 가장 중요한 요소가 되었다. 이러한 문제를 해결하기 위해 가연성의 유기 액체전해질이 불연성의 고체전해질로 대체된 전고체 전지를 제조하려는 연구들이 진행되고 있다. 그러나 고체전해질은 자체 이온전도도가 상대적으로 낮고 전극/전해질 계면에서 높은 저항이 발생하므로 실질적인 활용에 제약이 있었다. 이에 유무기 소재로 구성된 복합전해질은 고체전해질의 단점을 극복할 수 있는 대안으로 떠오르고 있다. 본 연구에서는 PEO 전해질과 LLZO 고체전해질을 복합화하여 전해질을 제조하였고, LLZO 고체전해질 함량에 따라 결정성, 형상 및 전기화학 성능 분석을 진행하였다. 결과로부터 PEO 전해질 내에 LLZO 고체전해질의 최적 함량 및 균일한 분포가 전체 복합전해질의 이온전도도 향상에 중요한 요소임을 확인하였다.

• 한국세라믹학회지
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• 제56권2호
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• pp.111-129
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• 2019

Recently, all-solid-state batteries (ASSBs) have attracted increasing interest owing to their higher energy density and safety. As the core material of ASSBs, the characteristics of the solid electrolyte largely determine the performance of the battery. Thus far, a variety of inorganic solid electrolytes have been studied, including the NASICON-type, LISICON-type, perovskite-type, garnet-type, glassy solid electrolyte, and so on. The garnet Li₇La₃Zr₂O₁₂ (LLZO) solid electrolyte is one of the most promising candidates because of its excellent comprehensively electrochemical performance. Both, experiments and theoretical calculations, show that cubic LLZO has high room-temperature ionic conductivity and good chemical stability while contacting with the lithium anode and most of the cathode materials. In this paper, the crystal structure, Li-ion transport mechanism, preparation method, and element doping of LLZO are introduced in detail based on the research progress in recent years. Then, the development prospects and challenges of LLZO as applied to ASSBs are discussed.

• 전기화학회지
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• 제25권3호
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• pp.105-112
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• 2022

전고체전지의 상용화를 위해서는 상온에서 작동이 가능한 고체전해질 개발이 필수적이며 이온전도도가 높은 물질을 채택하여 전고체전지를 제조해야 한다. 따라서, 기존의 옥사이드 계열의 고체의 이온전도도를 높이기 위하여 이종원소가 도핑된 Li₇La₃Zr₂O₁₂ (LLZO)를 필러소재(Al, Nb-LLZO)로 사용하였으며, 상온에서 작동이 가능하도록 Poly(ethylene oxide)/Poly(propylene carbonate) (PEO/PPC) 기반의 가넷형 무기계 고체고분자 전해질을 제조하였다. 이원금속 원소를 도핑한 가넷형 무기계 필러와 PEO/PPC (1:1 비율로 섞인) 고분자를 1:2.4의 비율로 균일하게 교반하여 전해질을 합성해 상온과 60 ℃에서 전고체 전지의 전기학적 성능을 분석하였다. 제조한 복합 전해질은 이원금속의 도핑으로 인하여 이온전도도가 향상되었으며, PEO 단독으로 사용하는 전해질보다 PPC를 1:1로 첨가하였을 때 이온전도도 향상을 도와 60 ℃ 뿐만 아니라 상온에서 전고체 전지의 용량과 용량 유지율이 개선되었음을 확인하였다.

• 한국세라믹학회지
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• 제54권4호
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• pp.278-284
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• 2017

In this work, Ta-substituted $Li_7La_3Zr_{2-x}O_{12}$ (LLZTO) powder and pellets with garnet cubic structure were fabricated and characterized by modified and optimized sol-gel synthesis. Ta-substituted LLZO powder with the smallest grain size and pure cubic structure with little pyrochlore phase was obtained by synthesis method in which Li and La sources in propanol solvent were mixed together with Zr and Ta sources in 2-methoxy ethanol. The LLZTO pellets made with the prepared powder showed cubic garnet structure for all conditions when the amount of Li addition was varied from 6.2 to 7.4 mol. All the X-ray peaks of the pyrochlore phase disappeared when the Li addition was increased above 7.0 mol. When the final sintering temperature was varied, the LLZTO pellet had a pyrochlore-mixed cubic phase above $1000^{\circ}C$. However, the surface morphology became much denser when the final sintering temperature was increased. The sol-gel-driven LLZTO pellet with a sintering temperature of $1100^{\circ}C$ showed a lithium ionic conductivity of 0.21 mS/cm when Au was adopted as electrode material for the blocking capacitor. The results of this study suggest that modified sol-gel synthesis is the optimum method to obtain cubic phase of LLZTO powder for highly dense and conductive solid electrolyte ceramics.

• Journal of Electrochemical Science and Technology
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• 제13권3호
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• pp.362-368
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• 2022

The application of polymer composite electrolyte in all-solid-state lithium-sulfur battery (ASSLSBs) can guarantee high energy density and improve the interface contact between electrolyte and electrode, which has a broader application prospect. However, the inherent insulation of the sulfur-cathode leads to a low electron/ion transfer rate. Carbon materials with high electronic conductivity and electrolyte materials with high ionic conductivity are usually selected to improve the electron/ion conduction of the composite cathode. In this work, PEO-LiTFSI-LLZO composite polymer electrolyte (CPE) with high ionic conductivity was prepared. The ionic conductivity was 1.16×10^-4 and 7.26×10^-4 S cm^-1 at 20 and 60℃, respectively. Meanwhile, the composite sulfur cathode was prepared with Sulfur, reduced graphene oxide and composite polymer electrolyte slurry (S-rGO-CPEs). In addition to improving the ion conductivity in the cathode, CPEs also replaces the role of binder. The influence of different contents of CPEs in the cathode material on the performance of the constructed battery was investigated. The results show that the electrochemical performance of the all-solid-state lithium-sulfur battery is the best when the content of the composite electrolyte in the cathode is 40%. Under the condition of 0.2C and 45℃, the charging and discharging capacity of the first cycle is 923 mAh g^-1, and the retention capacity is 653 mAh g^-1 after 50 cycles.

• Journal of Electrochemical Science and Technology
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• 제13권2호
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• pp.199-207
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• 2022

Lithium-sulfur batteries (LSBs) have emerged as a promising alternative to lithium-ion batteries (LIBs) owing to their high energy density and economic viability. In addition, all-solid-state LSBs, which use solid-state electrolytes, have been proposed to overcome the polysulfide shuttle effect while improving safety. However, the high interfacial resistance and poor ionic conductivity exhibited by the electrode and solid-state electrolytes, respectively, are significant challenges in the development of these LSBs. Herein, we apply a poly (ethylene oxide) (PEO)-based composite solid-state electrolyte with oxide Li₇La₃Zr₂O₁₂ (LLZO) solid-state electrolyte in an all-solid-state LSB to overcome these challenges. We use an electrochemical method to evaluate the degradation of the all-solid-state LSB in accordance with the carbon content and loading weight within the cathode. The all-solid-state LSB, with sulfur-carbon content in a ratio of 3:3, exhibited a high initial discharge capacity (1386 mAh g^-1), poor C-rate performance, and capacity retention of less than 50%. The all-solid-state LSB with a high loading weight exhibited a poor overall electrochemical performance. The factors influencing the electrochemical performance degradation were revealed through systematic analysis.

• Journal of Electrochemical Science and Technology
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• 제14권1호
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• pp.85-95
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• 2023

In recent years, solid-state Li metal batteries (SSLBs) have attracted significant attention as the next-generation batteries with high energy and power densities. However, uncontrolled dendrite growth and the resulting pulverization of Li during repeated plating/stripping processes must be addressed for practical applications. Herein, we report a plastic-crystal-based polymer/ceramic composite solid electrolyte (PCCE) to resolve these issues. To fabricate the one-side ceramic-incorporated PCCE (CI-PCCE) film, a mixed precursor solution comprising plastic-crystal-based polymer (succinonitrile, SN) with garnet-structured ceramic (Li₇La₃Zr₂O₁₂, LLZO) particles was infused into a thin cellulose membrane, which was used as a mechanical framework, and subsequently solidified by using UV-irradiation. The CI-PCCE exhibited good flexibility and a high room-temperature ionic conductivity of over 10^-3 S cm^-1. The Li symmetric cell assembled with CI-PCCE provided enhanced durability against Li dendrite penetration through the solid electrolyte (SE) layer than those with LLZO-free PCCEs and exhibited long-term cycling stability (over 200 h) for Li plating/stripping. The enhanced Li⁺ transference number and lower interfacial resistance of CI-PCCE indicate that the ceramic-polymer composite layer in contact with the Li anode enabled the uniform distribution of Li⁺ flux at the interface between the Li metal and CI-PCCE, thereby promoting uniform Li plating/stripping. Consequently, the Li//LiFePO₄ (LFP) full cell constructed with CI-PCCE demonstrated superior rate capability (~120 mAh g^-1 at 2 C) and stable cycle performance (80% after 100 cycles) than those with ceramic-free PCCE.

• Journal of the Korean Physical Society
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• 제73권10호
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• pp.1535-1540
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• 2018

In this study, we prepared and characterized Nb-doped $Li_7La_3Zr_{2-x}O_{12}$ (LLZNO) powder and pellets with a cubic garnet structure by using a modified sol-gel synthesis and hot pressing. LLZNO powder with a very small grain size and cubic structure without secondary phases could be obtained by using a synthesis method in which Li and La sources in a propanol solvent were mixed together with Zr and Nb sources in 2-methoxy ethanol. A pure cubic phase LLZNO pellet could be fabricated from the prepared LLZNO and an additional 6-wt% of $Li_2CO_3$ powder by hot pressing at $1050^{\circ}C$ and 15.8 MPa. The hot-pressed LLZNO pellet with a relative density of 99% exhibited a very dense surface morphology. The total Li ionic conductivity of the hot-pressed LLZNO was $7.4{\times}10^{-4}S/cm$ at room temperature, which is very high level compared to other reported values. The activation energy for ionic conduction was estimated to be 0.40 eV.