Oxide-Based Composite Electrolytes Using Na3Zr2Si2PO12/Na3PS4 Interfacial Ion Transfer.
Oxide-Based Composite Electrolytes Using Na3Zr2Si2PO12/Na3PS4 Interfacial Ion Transfer.
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DOI：
10.1021/acsami.8b02427
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发表时间：
2018-05
影响因子：
9.5
通讯作者：
Kousuke Noi;Yuka Nagata;T. Hakari;Kenji Suzuki;So Yubuchi;Yusuke Ito;A. Sakuda;A. Hayashi;
中科院分区：
文献类型：
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作者：
Kousuke Noi;Yuka Nagata;T. Hakari;Kenji Suzuki;So Yubuchi;Yusuke Ito;A. Sakuda;A. Hayashi;
使用Na3Zr2Si2PO12 (NASICON)固体电解质的全固态钠电池是安全且低成本的先进可充电电池系统的有希望的候选者。尽管 NASICON 电解质本质上具有高钠离子电导率，但其高烧结温度会干扰高性能电池的直接开发。在这项工作中，制备了具有 Na3PS4 (NPS) 玻璃陶瓷的免烧结 NASICON 基复合材料，结合了 NASICON 的高晶粒-体积电导率和 NPS 的界面形成能力。在复合材料制备之前，通过对 NASICON 烧结陶瓷和 NPS 玻璃薄膜之间的界面进行建模来研究 NASICON/NPS 界面电阻。室温以上界面离子转移阻力非常小； 25 和 100 °C 时的面积比电阻分别为 15.8 和 0.40 Ω cm2。在这种平稳的离子转移的基础上，通过球磨各组分的细粉制备了富含 NASICON (70-90 wt%) NASICON-NPS 复合粉末。复合粉末通过在室温下压制而致密化。扫描电子显微镜观察显示，致密 NPS 基质中高度分散的亚微米 NASICON 颗粒在氧化物和硫化物固体电解质之间形成封闭界面。含有 70 wt% 和 80 wt% NASICON 的复合生坯（未烧制）压块在 100 °C 时表现出较高的总电导率，分别为 1.1 × 10-3 和 6.8 × 10-4 S cm-1。采用 70 wt% NASICON 复合电解质，通过粉末材料的单轴压制构建全固态 Na15Sn4/TiS2 电池，并在 100 °C 下评估其放电性能。该电池在640 μA cm-2的电流密度下显示出约120 mAh g-1的可逆容量。所制备的氧化物基复合电解质成功应用于全固态钠充电电池，无需烧结。
All-solid-state sodium batteries using Na3Zr2Si2PO12 (NASICON) solid electrolytes are promising candidates for safe and low-cost advanced rechargeable battery systems. Although NASICON electrolytes have intrinsically high sodium-ion conductivities, their high sintering temperatures interfere with the immediate development of high-performance batteries. In this work, sintering-free NASICON-based composites with Na3PS4 (NPS) glass ceramics were prepared to combine the high grain-bulk conductivity of NASICON and the interfacial formation ability of NPS. Before the composite preparation, the NASICON/NPS interfacial resistance was investigated by modeling the interface between the NASICON sintered ceramic and the NPS glass thin film. The interfacial ion-transfer resistance was very small above room temperature; the area-specific resistances at 25 and 100 °C were 15.8 and 0.40 Ω cm2, respectively. On the basis of this smooth ion transfer, NASICON-rich (70-90 wt %) NASICON-NPS composite powders were prepared by ball-milling fine powders of each component. The composite powders were well-densified by pressing at room temperature. Scanning electron microscopy observation showed highly dispersed sub-micrometer NASICON grains in a dense NPS matrix to form closed interfaces between the oxide and sulfide solid electrolytes. The composite green (unfired) compacts with 70 and 80 wt % NASICON exhibited high total conductivities at 100 °C of 1.1 × 10-3 and 6.8 × 10-4 S cm-1, respectively. An all-solid-state Na15Sn4/TiS2 cell was constructed using the 70 wt % NASICON composite electrolyte by the uniaxial pressing of the powder materials, and its discharge properties were evaluated at 100 °C. The cell showed the reversible capacities of about 120 mAh g-1 under the current density of 640 μA cm-2. The prepared oxide-based composite electrolytes were thus successfully applied in all-solid-state sodium rechargeable batteries without sintering.