Flame-retardant quasi-solid polymer electrolyte enabling sodium metal batteries with highly safe characteristic and superior cycling stability
Flame-retardant quasi-solid polymer electrolyte enabling sodium metal batteries with highly safe characteristic and superior cycling stability
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阻燃准固体聚合物电解质使钠金属电池具有高安全特性和优异的循环稳定性
DOI：
10.1007/s12274-019-2369-9
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发表时间：
2019-03
期刊：
影响因子：
9.9
通讯作者：
Guanglei Cui
中科院分区：
文献类型：
--
作者：
Jinfeng Yang;Min Zhang;Zheng Chen;Xiaofan Du;Suqi Huang;Ben Tang;Tiantian Dong;Han Wu;Zhe Yu;Jianjun Zhang;Guanglei Cui
传统的液态电解质基钠金属电池存在电解质泄漏、易燃性和枝状钠沉积等严重的安全隐患。本文报道了一种以聚甲基乙烯醚-马来酸酐（P(MVE-alt-MA)）为主体，细菌纤维素（BC）为增强剂，磷酸三乙酯/碳酸乙烯酯/高氯酸钠（TEP/VC/NaClO4）为增塑剂的阻燃准固体聚合物电解质，用于高安全性钠金属电池。所制得的准固态聚合物电解质具有优异的阻燃性（1s内自熄）、完全的无泄漏性能和宽的电化学窗口（4.4 V）。更重要的是，使用这种聚合物电解质的Na3V2(PO4)3/Na金属电池具有优越的长期循环稳定性（1000次循环后容量保持率为84.4%），明显优于液体电解质（240次循环后容量保持率仅为2%）。此外，该阻燃准固体聚合物电解质为Na3V2(PO4)3/Na金属电池提供了良好的循环性能，在50℃下循环70次后容量保持率为80.2%，在- 10℃下循环50次后容量保持率为84.8%。即使在- 15°C下，该电池也显示出正常的充放电性能。这些令人着迷的循环性能主要归功于Na3V2(PO4)3阴极和金属钠阳极上形成的有效保护层。更深入的研究表明，这种阻燃型准固态聚合物电解质在先进的钠金属电池中具有多种功能：(1)参与形成良好的阴极电解质界面（CEI），抑制钒的溶解，保持Na3V2(PO4)3的结构完整性；(2)参与构建稳定的固体电解质界面（SEI），抑制Na枝晶的生长；(3)将阻燃性融入到聚合物钠电池中，增强耐燃性，消除电解液泄漏，从而提高钠电池的安全性。基于这些结果，我们进一步组装了能够承受恶劣条件（弯曲或切断角落）的Na3V2(PO4)3/ mos2袋电池，证实了所获得的聚合物电解质具有优异的不泄漏性能。总之，这些突出的特性将使这种阻燃准固体聚合物电解质成为高度安全的钠金属电池的一个非常有前途的候选者。
Conventional liquid electrolytes based sodium metal batteries suffer from severe safety hazards owing to electrolyte leakage, inflammability and dendritic sodium deposition. Herein, we report a flame-retardant quasi-solid polymer electrolyte with poly(methyl vinyl ether-alt-maleic anhydride) (P(MVE-alt-MA)) as host, bacterial cellulose (BC) as reinforcement, and triethyl phosphate/vinylene carbonate/sodium perchlorate (TEP/VC/NaClO4) as plasticizer for highly safe sodium metal batteries. The as-obtained quasi-solid polymer electrolyte exhibits superior flame retardancy (self-extinguish within 1 s), complete non-leakage property and wide electrochemical windows (4.4 V). More importantly, Na3V2(PO4)3/Na metal batteries using such polymer electrolyte delivers superior long-term cycling stability (84.4% capacity retention after 1000 cycles) which is significantly better than that (only 2% after 240 cycles) of liquid electrolyte. In addition, this flame-retardant quasi-solid polymer electrolyte provides favorable cycle performance (80.2% capacity retention after 70 cycles at 50 °C and 84.8% capacity retention after 50 cycles at −10 °C) for Na3V2(PO4)3/Na metal batteries. And this battery also displayed a normal charge/discharge property even at −15 °C. These fascinating cycle properties are mainly ascribed to the effective protective layers formed on Na3V2(PO4)3cathode and sodium metal anode. More thorough investigation elucidates that such flame-retardant quasi-solid polymer electrolyte plays a multifunctional role in the advanced sodium metal batteries: (1) Being involved in the formation of a favorable cathode electrolyte interface (CEI) to inhibit the dissolution of vanadium and maintain the structure integrity of the Na3V2(PO4)3; (2) Participating in building a stable solid electrolyte interface (SEI) to suppress the growth of Na dendrites; (3) Integrating flame-retardance into polymer sodium batteries to enhance flame-resistance, eliminate electrolyte leakage, and thus improve safety of sodium batteries. Based on these results, we further assembled Na3V2(PO4)3/MoS2pouch cell which can withstand harsh conditions (bended or cut off a corner), confirming the obtained polymer electrolyte with superior non-leakage property. In all, these outstanding characteristics would endow this flame-retardant quasi-solid polymer electrolyte a very promising candidate for highly-safe sodium metal batteries.
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影响因子：
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作者：
Zhizhen Zhang;Qiangqiang Zhang;C. Ren;F. Luo;Q. Ma;Yong‐Sheng Hu;Zhibin Zhou;Hong Li;Xuejie Hu
通讯作者：
Zhizhen Zhang;Qiangqiang Zhang;C. Ren;F. Luo;Q. Ma;Yong‐Sheng Hu;Zhibin Zhou;Hong Li;Xuejie Hu
基于不可燃有机磷酸盐电解质的更安全钠离子电池
影响因子：
15.1
作者：
Zeng, Ziqi;Jiang, Xiaoyu;Li, Ran;Yuan, Dingding;Ai, Xinping;Yang, Hanxi;Cao, Yuliang
通讯作者：
Cao, Yuliang
影响因子：
13.6
作者：
Tikekar MD;Archer LA;Koch DL
通讯作者：
Koch DL
影响因子：
3.7
作者：
Bo Zhang;M. Metzger;S. Solchenbach;Martin Payne;Stefano Meini;H. Gasteiger;A. Garsuch;B. Lucht-
通讯作者：
Bo Zhang;M. Metzger;S. Solchenbach;Martin Payne;Stefano Meini;H. Gasteiger;A. Garsuch;B. Lucht-
DOI：
10.1149/2.jes111637
发表时间：
2011-08
期刊：
--
影响因子：
--
作者：
X. Xia;M. Obrovac;J. Dahn
通讯作者：
X. Xia;M. Obrovac;J. Dahn