碳包覆对水系磷酸钛钠电化学性能的影响
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摘要
采用溶胶-凝胶法制备了纳米级磷酸钛钠(NaTi_2(PO_4)_3),以聚乙烯醇为碳源对其进行碳包覆,研究了碳包覆量对NaTi_2(PO_4)_3/C负极在硫酸钠水溶液中电化学性能的影响。结果表明,合成的NaTi_2(PO_4)_3材料为纳米级晶粒聚集而成。碳包覆量3.6%的NaTi_2(PO_4)_3/C电极表面包覆得较为均匀,表现出最佳的电化学性能。在高达4 C的倍率下,基于钠离子嵌入/脱出的首次放电比容量达到119 m Ah/g,循环20次后容量未见明显衰减,受析氢副反应等影响库仑效率缓慢降低,这与碳包覆表面的破坏,NaTi_2(PO_4)_3在水溶液中的结构变化有关。
Sodium titanium phosphate( NaTi_2(PO_4)_3) anode materials are synthesized by sol-gel method and heat treatment in air. Polyvinyl alcohol is used as the carbon source to coat NaTi_2( PO_4)_3 by temperature-programmed calcination under nitrogen atmosphere. The crystalline structure and morphology of these materials are characterized by Xray diffraction and SEM. Electrochemical performance of the carbon coated NaTi_2( PO_4)_3with different carbon contents are investigated in 1. 0 mol / L Na_2SO_4 aqueous solution by using cyclic voltammetry and galvanostatic charge-discharge measurement. The results show that NaTi_2( PO_4)_3 exhibits about 80 nm of nano-sized crystalline with rhombohedral structure. The excellent electrochemical performance of the carbon coated NaTi_2( PO_4)_3 could be achieved with 3. 6% of carbon coating. The initial discharge capacity is 119. 0 m Ah / g and there is almost no capacity degradation after 20 cycles at a 4C rate charge-discharge. Butthe columbic efficiency degrades slowly with charge-discharge cycles.
Sodium titanium phosphate( NaTi_2(PO_4)_3) anode materials are synthesized by sol-gel method and heat treatment in air. Polyvinyl alcohol is used as the carbon source to coat NaTi_2( PO_4)_3 by temperature-programmed calcination under nitrogen atmosphere. The crystalline structure and morphology of these materials are characterized by Xray diffraction and SEM. Electrochemical performance of the carbon coated NaTi_2( PO_4)_3with different carbon contents are investigated in 1. 0 mol / L Na_2SO_4 aqueous solution by using cyclic voltammetry and galvanostatic charge-discharge measurement. The results show that NaTi_2( PO_4)_3 exhibits about 80 nm of nano-sized crystalline with rhombohedral structure. The excellent electrochemical performance of the carbon coated NaTi_2( PO_4)_3 could be achieved with 3. 6% of carbon coating. The initial discharge capacity is 119. 0 m Ah / g and there is almost no capacity degradation after 20 cycles at a 4C rate charge-discharge. Butthe columbic efficiency degrades slowly with charge-discharge cycles.
引文
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[19]赵平,文越华,程杰,等.水系锂离子电池负极材料Li Ti2(PO4)3/C的合成与电化学性能[J].高等学校化学学报,2015,36(6):1180-1186.
[2]杜柯,胡国荣.锂离子电池正极材料富锂锰基固溶体的研究进展[J].科学通报,2012,57(10):794-804.
[3]Marion Perrin,Philippe Malbranche,Elisabeth Lemaire-Potteau,et al.Temperature behaviour:Comparison for nine storage technologies Results from the INVESTIRE Network[J].Journal of Power Sources,2006,154:545-549.
[4]李佳,何亮明,杜翀.锂离子电池高温储存后的安全性能[J].电池,2010,40(3):158-160.
[5]吴凯,张耀,曾毓群,等.锂离子电池安全性能研究[J].化学进展,2011,23(2/3):401-409.
[6]夏兰,李素丽,艾新平,等.锂离子电池的安全性技术[J].化学进展,2011,23(2/3):328-335.
[7]杨汉西,钱江锋.水溶液钠离子电池及其关键材料的研究进展[J].无机材料学报,2013,28(11):1165-1171.
[8]Haegyeom Kim,Jihyun Hong,Kyu-Young Park,et al.Aqueous Rechargeable Li and Na Ion Batteries,dx.doi.org/10.1021/cr500232y[J].Chem Rev,2014,114(23):11788-11827.
[9]Deng C,Zhang S,Dong Z,et al.1D nanostructured sodium vanadium oxide as a novel anode material for aqueous sodium ionbatteries[J].Nano Energy,2014,4:49-55.
[10]Vujkovi'c M,Sljuki'c Paunkovi'c B,Stojkovi'c I,et al.Versatile insertion capability of Na1.2V3O8nanobelts in aqueous electrolyte solutions[J].Electrochimica Acta,2014,147:167-175.
[11]Wu Xianyong,Cao Yuliang,Ai Xinping,et al.A low-cost and environmentally benign aqueous rechargeable sodium-ion battery based on Na Ti2(PO4)3-Na2Ni Fe(CN)6intercalation chemistry[J].Electrochemistry Communications,2013,31:145-148.
[12]Nagasubramanian Arun,Vanchiappan Aravindan,Wong Chui Ling,et al.Carbon coated Li Ti2(PO4)3as new insertion anode for aqueous Na-ion batteries[J].Journal of Alloys and Compounds,2014,603:48-51.
[13]Zheng Li,Dorthe B Ravnsbk,Kai Xiang,et al.Na3Ti2(PO4)3as a sodium-bearing anode for rechargeable aqueous sodium-ion batteries[J].Electrochemistry Communications,2014,44:12-15.
[14]Milica Vujkovi'c,Miodrag Mitri'c,Slavko Mentus.High-rate intercalation capability of Na Ti2(PO4)3/C composite in aqueous lithium and sodium nitrate solutions[J].Journal of Power Sources,2015,288:176-186.
[15]Luo J Y,Xia Y Y.Aqueous lithium-ion battery Li Ti2(PO4)3/Li Mn2O4:with high power and energy densities as well as superior cycling stability[J].Adv Func Mater,2007,17:3877-3884.
[16]张乃庆,李伟,柳志民,等.水系电解质锂离子电池研究[J].稀有金属材料与工程,2012,41(2):372-376.
[17]Colin Wessells,Fabio La Mantia,Heather Deshazer,et al.Synthesis and electrochemical performance of a lithium titanium phosphate anode for aqueous lithium-ion batteries[J].Journal of the Electrochemical Society,2011,158(3):A352-A355.
[18]Cullity B D.Elements of X-ray Diffraction[M].2nd ed.New Jersey:Addison-Wesley,Reading,MA,1978.
[19]赵平,文越华,程杰,等.水系锂离子电池负极材料Li Ti2(PO4)3/C的合成与电化学性能[J].高等学校化学学报,2015,36(6):1180-1186.