新型Na/CF<sub><em>x</em></sub>可充电池催化剂的制备与性能

摘要类似于锂/氟化碳（Li/CF_x）电池，钠/氟化碳（Na/CF_x）电池具有低廉的价格和较高的能量密度，是未来锂离子电池的理想替代选项。但是Na/CF_x电池目前还存在着极化大和循环性能差等问题。为解决以上问题，在CF_x阴极中加入催化剂成为改善电池电化学性能的一个重要途径。分别采用水热法和溶胶-凝胶法制备了催化剂材料Co₃O₄-TiO₂和ZrO₂，并对其进行了表征。分别将TiO₂、Co₃O₄、Co₃O₄-TiO₂以及ZrO₂ 4种催化剂材料按10%（质量比，下同）加入CF_x正极中并组装成电池，然后对电池进行了恒流充放电、交流阻抗以及循环伏安等电化学性能测试。实验结果表明，加入4种催化剂后，Na/CF_x电池的放电比容量得到明显提升。其中，ZrO₂催化剂表现出最佳的催化性能。经过100次后循环后，含有ZrO₂的Na/CF_x电池的放电比容量为167.3 mAh·g^-1，极大地改善了钠/氟化碳电池的循环性能。

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	刘梓洋
	钟学奇
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	刘兴江
	徐强

关键词： Na/CF_x电池催化剂极化过渡金属氧化物循环性能

Abstract： Similar to lithium/fluorocarbon (Li/CF_x) battery, sodium/fluorocarbon (Na/CF_x) battery has low price and high energy density, so it is an ideal alternative for lithium-ion battery in the future. Nevertheless, the battery has some problems needing to be resolved until now, such as high polarization and poor cycle performance. In order to solve the above problems, the addition of catalysts in CF_x cathode is an important way to improve the electrochemical performance of cells. In this paper, the catalyst materials of Co₃O₄-TiO₂ and ZrO₂ have been prepared by the hydrothermal and sol-gel methods, respectively, which are characterized subsequently. Four catalyst materials of TiO₂ Co₃O₄, Co₃O₄-TiO₂ and ZrO₂ are added into the positive electrode of CF_x at the mass ratio of 10%, and then are assembled into the batteries, respectively. The electrochemical performances of these batteries are tested by way of constant current charge, discharge impedance and cyclic voltammetry. The experimental results show that the discharge specific capacity of Na/CF_x batteries has been increased significantly after the addition of catalysts. Among these catalysts, ZrO₂ catalyst reveals the best catalytic performance. The cycle performance of Na/CF_x battery has been increased after addition of ZrO₂ catalyst, and the specific discharge capacity of the Na/CF_x battery may reach 167.3 mAh·g^-1 after 100 cycles.

Keywords： Na/CF_x battery； catalysts； polarization； transition metal oxide； cyclic performance

Received 2019-07-10;

Fund:天津市自然科学基金（17JCYBJC20900）。

Corresponding Authors: 徐强,E-mail:xuqiang@tju.edu.cn。 Email: xuqiang@tju.edu.cn

About author: 刘梓洋(1994-),男,硕士研究生,主要从事化学电源领域的研究工作。

引用本文:

刘梓洋, 钟学奇, 张硕卿, 丁飞, 刘兴江, 徐强.新型Na/CF_x可充电池催化剂的制备与性能[J]. 化学工业与工程, 2020,37(5): 64-71,79

Liu Ziyang, Zhong Xueqi, Zhang Shuoqing, Ding Fei, Liu Xingjiang, Xu Qiang.Preparation and Properties of Novel Catalysts for Rechargeable Na/CF_x Batteries[J]. Chemcial Industry and Engineering, 2020,37(5): 64-71,79

[1] Whittingham M S. Lithium batteries and cathode materials[J]. Chemical Reviews, 2004, 104(10):4271-4302
[2] Xu W, Wang J, Ding F, et al. Lithium metal anodes for rechargeable batteries[J]. Energy & Environmental Science, 2013, 7(2):513-537
[3] Jeong G, Kim Y U, Kim H, et al. Prospective materials and applications for Li secondary batteries[J]. Energy & Environmental Science, 2011, 4(6):1986-2002
[4] Li C, Yin C, Mu X, et al. Top-Down synthesis of open framework fluoride for lithium and sodium batteries[J]. Chemistry of Materials, 2013, 25(6):962-969
[5] Gheytani S, Liang Y, Wu F, et al. An aqueous Ca-ion battery[J]. Advanced Science, 2017, doi:10.1002/advs.201700465
[6] 王昊, 邓邦为, 葛武杰, 等. 普鲁士蓝类材料在钠离子电池中的研究进展[J]. 化学进展, 2017, 29(6):683-694 Wang Hao, Deng Bangwei, Ge Wujie, et al. Recent advances in Prussian blue analogues materials for sodium-ion batteries[J]. Progress in Chemistry, 2017, 29(6):683-694(in Chinese)
[7] Ahmad Y, Guérin K, Dubois M, et al. Enhanced performances in primary lithium batteries of fluorinated carbon nanofibres through static fluorination[J]. Electrochimica Acta, 2013, 114:142-151
[8] 李亚寅, 杨李娜. 锂氟化碳电池正极材料氟化石墨的改性技术[J]. 信息系统工程, 2018,(3):92-94
[9] Nishijima M, Gocheva I D, Okada S, et al. Cathode properties of metal trifluorides in Li and Na secondary batteries[J]. Journal of Power Sources, 2009, 190(2):558-562
[10] Kim S W, Seo D H, Gwon H, et al. Fabrication of FeF₃ nanoflowers on CNT branches and their application to high power lithium rechargeable batteries[J]. Advanced Materials, 2010, 22(46):5260-5264
[11] Li C, Yin C, Gu L, et al. An FeF₃·0.5H₂O polytype:A microporous framework compound with intersecting tunnels for Li and Na batteries[J]. Journal of the American Chemical Society, 2013, 135(31):11425-11428
[12] Liu W, Li H, Xie J, et al. Rechargeable room-temperature CF_x-sodium battery[J]. ACS Applied Materials & Interfaces, 2014, 6(4):2209-2212
[13] Liu W, Zhan B, Shi B, et al. Sandwich-Like structure of carbon fluoride/graphene oxide/polyacrylonitrile cathode for lithium and sodium batteries[J]. ChemElectroChem, 2017, 4(2):436-440
[14] Shao Y, Yue H, Qiao R, et al. Synthesis and reaction mechanism of novel fluorinated carbon fiber as a high-voltage cathode material for rechargeable Na batteries[J]. Chemistry of Materials, 2016, 28(4):1026-1033
[15] Liu W, Li Y, Zhan B, et al. Amorphous, highly disordered carbon fluorides as a novel cathode for sodium secondary batteries[J]. The Journal of Physical Chemistry C, 2016, 120(44):25203-25209
[16] Liu W, Shadike Z, Liu Z C, et al. Enhanced electrochemical activity of rechargeable carbon fluorides-sodium battery with catalysts[J]. Carbon, 2015, 93:523-532
[17] Chayambuka K, Mulder G, Danilov D, et al. Sodium-ion battery materials and electrochemical properties reviewed[J]. Advanced Energy Materials, 2018, doi:10.1002/aenm.201800079
[18] Liu W, Wang Y, Li Y, et al. Long-Life sodium/carbon fluoride batteries with flexible, binder-free fluorinated mesocarbon microbead film electrodes[J]. Chemical Communications, 2018, doi:10.1039/C7CC08349A
[19] Lu Y, Gallant B M, Kwabi D G, et al. Lithium-Oxygen batteries:Bridging mechanistic understanding and battery performance[J]. Energy & Environmental Science, 2013, 6(3):750-768
[20] Bruce P G, Freunberger S A, Hardwick L J, et al. Li-O₂ and Li-S batteries with high energy storage[J]. Nature Materials, 2011, 11(1):19-29
[21] Fu W, Zhao E, Sun Z, et al. Iron fluoride-carbon nanocomposite nanofibers as free-standing cathodes for high-energy lithium batteries[J]. Advanced Functional Materials, 2018, doi:10.1002/adfm.201801711
[22] 郝明明, 丁飞, 张晶, 等. 锂氟化碳电池电解液研究[J]. 电源技术, 2018, 42(6):821-824 Hao Mingming, Ding Fei, Zhang Jing, et al. Research on electrolyte of Li-CF_x battery[J]. Chinese Journal of Power Sources, 2018, 42(6):821-824(in Chinese)
[23] Goyenola C, Stafström S, Schmidt S, et al. Carbon fluoride, CF_x: Structural diversity as predicted by first principles[J]. The Journal of Physical Chemistry C, 2014, 118(12):6514-6521
[24] Fulvio P F, Brown S S, Adcock J, et al. Low-Temperature fluorination of soft-templated mesoporous carbons for a high-power lithium/carbon fluoride battery[J]. Chemistry of Materials, 2011, 23(20):4420-4427
[25] Yao J, Pan Q, Yao S, et al. Mesoporous MnO₂ nanosphere/graphene sheets as electrodes for supercapacitor synthesized by a simple and inexpensive reflux reaction[J]. Electrochimica Acta, 2017, 238:30-35