• Title/Summary/Keyword: Sulfide-based solid electrolytes

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Design Principles for Moisture-Tolerant Sulfide-Based Solid Electrolytes and Associated Effect on the Electrochemical Performance of All-Solid-State Battery

  • Ohmin Kwon;Se Young Kim;Jinyeon Hwang;Jonghyun Han;Seungho Yu;Taeeun Yim;Si Hyoung Oh
    • Journal of Electrochemical Science and Technology
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    • v.15 no.4
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    • pp.437-458
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    • 2024
  • The grave concern on the safety of Li-ion batteries adopted in commercial electrical vehicles pushes an urgent demand for developing safer all-solid-state batteries (ASSBs), where ion-conducting solid electrolytes play pivotal roles. Much higher conductivity and more ductile nature of sulfide-based electrolytes offers great advantages over conventional oxide materials in terms of manufacturing process difficulty and the battery performance. However, instability of sulfide materials towards atmospheric moisture results in the substantial degradation in the ionic conductivity and the release of hazardous gas. After over a decade of intensive research, various customized strategies based on the specific design rules were developed for each electrolyte to tackle this crucial issue. However, in most cases a moisture tolerance was endowed only after compromising its vital ionic conductivity to some extent. Nevertheless, the actual applications of sulfide electrolytes to ASSBs often lead to improved battery performance by virtue of the interfacial stabilization between oxide-based cathode materials and sulfide-based solid electrolytes. Therefore, it is essential to fully comprehend the critical factors of each atmospheric stabilization technology that potentially affects the eventual battery performance. Herein, we go over the current status of state-of-the-art moisture-stabilizing technologies for each sulfide-based solid electrolyte, summarizing the major effect of each technology on the various aspect of the electrochemical performance upon application. We believe that this review will contribute to achieving effective moisture-stabilization of sulfide-based solid electrolytes, catalyzing the successful commercialization of sulfide-based ASSBs.

A Review of Inorganic Solid Electrolytes for All-Solid-State Lithium Batteries: Challenges and Progress

  • Seul Ki Choi;Jaehun Han;Gi Jeong Kim;Yeon Hee Kim;Jaewon Choi;MinHo Yang
    • Journal of Powder Materials
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    • v.31 no.4
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    • pp.293-301
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    • 2024
  • All-solid-state lithium batteries (ASSLBs) are receiving attention as a prospective next-generation secondary battery technology that can reduce the risk of commercial lithium-ion batteries by replacing flammable organic liquid electrolytes with non-flammable solid electrolytes. The practical application of ASSLBs requires developing robust solid electrolytes that possess ionic conductivity at room temperature on a par with that of organic liquids. These solid electrolytes must also be thermally and chemically stable, as well as compatible with electrode materials. Inorganic solid electrolytes, including oxide and sulfide-based compounds, are being studied as promising future candidates for ASSLBs due to their higher ionic conductivity and thermal stability than polymer electrolytes. Here, we present the challenges currently facing the development of oxide and sulfide-based solid electrolytes, as well as the research efforts underway aiming to resolve these challenges.

Electrochemical Properties of Cathode according to the Type of Sulfide Electrolyte and the Application of Surface Coating

  • Yoon, Da Hye;Park, Yong Joon
    • Journal of Electrochemical Science and Technology
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    • v.12 no.1
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    • pp.126-136
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    • 2021
  • The electrochemical performance of all-solid-state cells (ASSCs) based on sulfide electrolytes is critically affected by the undesirable interfacial reactions between oxide cathodes and sulfide electrolytes because of the high reactivity of sulfide electrolytes. Based on the concept that the interfacial reactions are highly dependent on the type of sulfide electrolyte, the electrochemical properties of the ASSCs prepared using three types of sulfide electrolytes were observed and compared. The Li2MoO4-LiI coating layer was also introduced to suppress the interfacial reactions. The cells using argyrodite electrolyte exhibited a higher capacity and Coulombic efficiency than the cells using 75Li2S-22P2S5-3Li2SO4 and Li7P3S11 electrolytes, indicating that the argyrodite electrolyte is less reactive with cathodes than other electrolytes. Moreover, the introduction of Li2MoO4-LiI coating on the cathode surface significantly enhanced the electrochemical performance of ASSCs because of the protection of coating layer. Pulverization of argyrodite electrolyte is also effective in increasing the capacity of cells because the smaller size of electrolyte particles improved the contact stability between the cathode and the sulfide electrolyte. The cyclic performance of cells was also enhanced by pulverized electrolyte, which is also associated with improved contact stability at the cathode/electrolyte. These results show that the introduction of Li2MoO4-LiI coating and the use of pulverized sulfide electrolyte can exhibit a synergic effect of suppressed interfacial reaction by the coating layer and improved contact stability owing to the small particle size of electrolyte.

Modified Lithium Borate Buffer Layer for Cathode/Sulfide Electrolyte Interface Stabilization

  • Dae Ik Jang;Yong Joon Park
    • Journal of Electrochemical Science and Technology
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    • v.15 no.4
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    • pp.530-540
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    • 2024
  • All-solid-state rechargeable batteries, using nonflammable sulfide-based solid electrolytes, address lithium-ion battery safety issues while enhancing energy density and operating temperature range. However, the electrochemical stability limitations of sulfide electrolytes present challenges to the interface stability, particularly with oxide-based cathodes. The application of a stable coating layer is known to be effective for stabilizing the cathode/sulfide electrolyte interface. In particular, lithium borate is a promising coating material owing to its cost-effectiveness and efficiency in controlling interfacial reactions. However, lithium borate exhibits oxide characteristics, leading to a difference in the chemical potential of Li+ compared to sulfide electrolytes. This discrepancy results in an uneven distribution of Li+ ions at the interface, which hinders Li-ion migration during charge and discharge cycles. To address this issue, a lithium borate-coating layer was modified with sulfur via a gaseous reaction involving sulfur. Sulfur-modified lithium borate is expected to reduce the chemical potential difference of Li+ and enhance the electrochemical properties. To confirm the effectiveness of sulfur modification, the electrochemical properties of coated and pristine samples were compared via various analysis tools. The results confirmed that sulfur modification can further improve the effect of lithium borate coating in enhancing the rate capability and cyclic performance of a battery. Additionally, it was observed that sulfur modification further reduces interfacial resistance and considerably improves the control of side reactions.

Research progress of oxide solid electrolytes for next-generation Li-ion batteries (차세대 리튬이차전지를 위한 산화물 고체전해질의 연구동향)

  • Kang, Byoungwoo;Park, Heetaek;Woo, Seungjun;Kang, Minseok;Kim, Abin
    • Ceramist
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    • v.21 no.4
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    • pp.349-365
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    • 2018
  • Since the electrification of vehicles has been extended, solid-state batteries have been attracting a lot of interest because of their superior safety. Especially, polymer, sulfide, and oxide based materials are being studied as solid electrolytes, and each type of materials has advantaged and disadvantages over others. Oxide electrolytes has higher chemical and electrochemical stability compared to the other types of electrolytes. However, ionic conductivity isn't high enough as much as that of organic liquid electrolytes. Also, there are many difficulties of fabricating solid-state batteries with oxide based electrolytes because they require a sintering process at very high temperature (above ${\sim}800^{\circ}C$). Herein, we review recent studies of solid-state batteries with oxide based electrolytes about the ionic conductivity, interfacial reactions with Li metal, and preparation of solid-state cell.

Enhanced Cathode/Sulfide Electrolyte Interface Stability Using an Li2ZrO3 Coating for All-Solid-State Batteries

  • Lee, Jun Won;Park, Yong Joon
    • Journal of Electrochemical Science and Technology
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    • v.9 no.3
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    • pp.176-183
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    • 2018
  • In this study, a $Li_2ZrO_3$ coated $Li[Ni_{0.8}Co_{0.15}Al_{0.05}]O_2$ (NCA) cathode was applied to an all-solid-state cell employing a sulfide-based solid electrolyte. Sulfide-based solid electrolytes are preferable for all-solid-state cells because of their high ionic conductivity and good softness and elasticity. However, sulfides are very reactive with oxide cathodes, and this reduces the stability of the cathode/electrolyte interface of all-solid-state cells. $Li_2ZrO_3$ is expected to be a suitable coating material for the cathode because it can suppress the undesirable reactions at the cathode/sulfide electrolyte interface because of its good stability and high ionic conductivity. Cells employing $Li_2ZrO_3$ coated NCA showed superior capacity to those employing pristine NCA. Analysis by X-ray photoelectron spectroscopy and electron energy loss spectroscopy confirmed that the $Li_2ZrO_3$ coating layer suppresses the propagation of S and P into the cathode and the reaction between the cathode and the sulfide solid electrolyte. These results show that $Li_2ZrO_3$ coating is promising for reducing undesirable side reactions at the cathode/electrolyte interface of all-solid-state-cells.

Li3PO4 Coated Li[Ni0.75Co0.1Mn0.15]O2 Cathode for All-Solid-State Batteries Based on Sulfide Electrolyte

  • Lee, Joo Young;Park, Yong Joon
    • Journal of Electrochemical Science and Technology
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    • v.13 no.3
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    • pp.407-415
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    • 2022
  • Surface coating of cathodes is an essential process for all-solid-state batteries (ASSBs) based on sulfide electrolytes as it efficiently suppresses interfacial reactions between oxide cathodes and sulfide electrolytes. Based on computational calculations, Li3PO4 has been suggested as a promising coating material because of its higher stability with sulfides and its optimal ionic conductivity. However, it has hardly been applied to the coating of ASSBs due to the absence of a suitable coating process, including the selection of source material that is compatible with ASSBs. In this study, polyphosphoric acid (PPA) and (NH4)2HPO4 were used as source materials for preparing a Li3PO4 coating for ASSBs, and the properties of the coating layer and coated cathodes were compared. The Li3PO4 layer fabricated using the (NH4)2HPO4 source was rough and inhomogeneous, which is not suitable for the protection of the cathodes. Moreover, the water-based coating solution with the (NH4)2HPO4 source can deteriorate the electrochemical performance of high-Ni cathodes that are vulnerable to water. In contrast, when an alcohol-based solvent was used, the PPA source enabled the formation of a thin and homogeneous coating layer on the cathode surface. As a consequence, the ASSBs containing the Li3PO4-coated cathode prepared by the PPA source exhibited significantly enhanced discharge and rate capabilities compared to ASSBs containing a pristine cathode or Li3PO4-coated cathode prepared by the (NH4)2HPO4 source.

Effects of binary conductive additives on electrochemical performance of a sheet-type composite cathode with different weight ratios of LiNi0.6Co0.2Mn0.2O2 in all-solid-state lithium batteries

  • Ann, Jiu;Choi, Sunho;Do, Jiyae;Lim, Seungwoo;Shin, Dongwook
    • Journal of Ceramic Processing Research
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    • v.19 no.5
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    • pp.413-418
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    • 2018
  • All-solid-state lithium batteries (ASSBs) using inorganic sulfide-based solid electrolytes are considered prospective alternatives to existing liquid electrolyte-based batteries owing to benefits such as non-flammability. However, it is difficult to form a favorable solid-solid interface among electrode constituents because all the constituents are solid particles. It is important to form an effective electron conduction network in composite cathode while increasing utilization of active materials and not blocking the lithium ion path, resulting in excellent cell performance. In this study, a mixture of fibrous VGCF and spherical nano-sized Super P was used to improve rate performance by fabricating valid conduction paths in composite cathodes. Then, composite cathodes of ASSBs containing 70% and 80% active materials ($LiNi_{0.6}Co_{0.2}Mn_{0.2}O_2$) were prepared by a solution-based process to achieve uniform dispersion of the electrode components in the slurry. We investigated the influence of binary carbon additives in the cathode of all-solid-state batteries to improve rate performance by constructing an effective electron conduction network.

Sintering Behavior of Borate-Based Glass Ceramic Solid Electrolytes for All-Solid Batteries (전고체전지용 붕산염 유리 세라믹 고체 전해질의 조성비에 따른 소결 특성 연구)

  • Jeong Min Lee;Dong Seok Cheong;Sung Hyun Kang;Tirtha Raj Acharya;Eun Ha Choi;Weon Ho Shin
    • Journal of the Korean Institute of Electrical and Electronic Material Engineers
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    • v.37 no.4
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    • pp.445-450
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    • 2024
  • The expansion of lithium-ion battery usage beyond portable electronic devices to electric vehicles and energy storage systems is driven by their high energy density and favorable cycle characteristics. Enhancing the stability and performance of these batteries involves exploring solid electrolytes as alternatives to liquid ones. While sulfide-based solid electrolytes have received significant attention for commercialization, research on amorphous-phase glass solid electrolytes in oxide-based systems remains limited. Here, we investigate the glass transition temperatures and sintering behaviors by changing the molecular ratio of Li2O/B2O3 in borate glass comprising Li2O-B2O3-Al2O3 system. The glass transition temperature is decreasing as increasing the amount of Li2O. When we sintered at 450℃, just above the glass transition temperature, the samples did not consolidate well, while the proper sintered samples could be obtained under the higher temperature. We successfully obtained the borate glass ceramics phases by melt-quenching method, and the sintering characteristics are investigated. Future studies could explore optimizing ion conductivity through refining processing conditions, adjusting the glass former-to-modifier ratio, and incorporating additional Li salt to enhance the ionic conductivity.

Evaluations of Thermal Diffusivity and Electrochemical Properties for Lithium Hydride and Electrolyte Composites (리튬계 수소화물 전해질 복합막의 열확산 및 전기화학적 특성평가)

  • Hwang, June-Hyeon;Hong, Tae-Whan
    • Korean Journal of Materials Research
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    • v.32 no.10
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    • pp.429-434
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    • 2022
  • There is ongoing research to develop lithium ion batteries as sustainable energy sources. Because of safety problems, solid state batteries, where electrolytes are replaced with solids, are attracting attention. Sulfide electrolytes, with a high ion conductivity of 10-3 S/cm or more, have the highest potential performance, but the price of the main materials is high. This study investigated lithium hydride materials, which offer economic advantages and low density. To analyze the change in ion conductivity in polymer electrolyte composites, PVDF, a representative polymer substance was used at a certain mass ratio. XRD, SEM, and BET were performed for metallurgical analyses of the materials, and ion conductivity was calculated through the EIS method. In addition, thermal conductivity was measured to analyze thermal stability, which is a major parameter of lithium ion batteries. As a result, the ion conductivity of LiH was found to be 10-6 S/cm, and the ion conductivity further decreased as the PVDF ratio increased when the composite was formed.