High‐Voltage Operation of All‐Oxide Solid‐State Sodium Batteries Using NASICON‐Related Materials
High‐Voltage Operation of All‐Oxide Solid‐State Sodium Batteries Using NASICON‐Related Materials
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使用 NASICON 相关材料的全氧化物固态钠电池的高电压运行
DOI：
10.1002/batt.202300075
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发表时间：
2023
期刊：
影响因子：
--
通讯作者：
Kobayashi Takeshi
中科院分区：
文献类型：
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作者：
Kutsuzawa Dai;Kobayashi Takeshi
全氧化物固态钠电池（AOSSSB）由氧化物电解质和含钠离子载体的氧化物活性材料组成，因其高安全性和材料丰富性而备受关注。然而，AOSSSB的工作电压不可避免地低，因为可用于AOSSSB的活性材料的数量受到高温制造期间电解质/电极界面处的不期望的反应的限制。在此，我们使用Na超离子导体型固体电解质Na 3 Zr 2（SiO 4）2（PO 4）（NZSP）、Na超离子导体型负极活性材料NaTi 2（PO 4）3和混合磷酸盐正极活性材料Na 4 Ni 3（PO 4）2（P2 O 7）通过Na 2B 4 O 7·10 H2O辅助低温制造技术制造AOSSSB。所获得的NaTi 2（PO 4）3/NZSP/Na 4 Ni 3（PO 4）2（P2 O 7）电池表现出3.1V的平均放电电压，这是AOSSSB中所报道的最高电压。 此外，与原始NZSP相比，含Na 2B 4 O 7·10 H2O的NZSP电解质显示出更宽的电化学窗口，使电池能够承受宽电压操作（在0-5.1 V下10次充电/放电循环后，容量保持率为71%）。
All‐oxide solid‐state sodium batteries (AOSSSBs), which are composed of oxide electrolytes and oxide active materials with sodium‐ion carriers, have attracted attention because of their high safety and material abundance. However, the operating voltage of AOSSSBs is inevitably low because the number of active materials available for use in AOSSSBs is restricted by undesirable reactions at electrolyte/electrode interfaces during high‐temperature fabrication. Herein, we fabricate AOSSSBs using a Na superionic conductor‐type solid electrolyte Na3Zr2(SiO4)2(PO4) (NZSP), a Na superionic conductor‐type negative active material NaTi2(PO4)3, and a mixed‐phosphate cathode active material Na4Ni3(PO4)2(P2O7) by a Na2B4O7⋅ 10H2O‐assisted low‐temperature fabrication technique. The obtained NaTi2(PO4)3/NZSP/Na4Ni3(PO4)2(P2O7) batteries exhibit an average discharge voltage of 3.1 V, which is the highest voltage ever reported in AOSSSBs. In addition, Na2B4O7⋅ 10H2O‐containing NZSP electrolytes show a wider electrochemical window in comparison with the pristine NZSP, enabling the batteries to endure a wide voltage operation (a capacity retention of 71 % after 10 cycles of charge/discharge in 0–5.1 V).