化工新型材料

化工新型材料 ›› 2019, Vol. 47 ›› Issue (6) : 126-130.

科学研究

Mn²⁺、Ti⁴⁺掺杂对Li₂FeSiO₄/C正极材料电化学性能的影响

作者信息 +

Influence of Mn²⁺ and Ti⁴⁺ doping on the electrochemical property of Li₂FeSiO₄/C

Liu Ping, Gong Yong, Li Lin, Dai Zuyang, Gu Qilong, Cheng Wei, Chen Jian

Author information +

文章历史 +

Received		Published
2018-01-26		2019-06-20
Issue Date	Revised Date
2019-07-05	2018-01-26

PDF (4316K)

摘要

针对锂离子电池正极材料Li₂FeSiO₄导电率和锂离子扩散率低的缺点,采用溶胶凝胶-微波法合成纳米复合材料硅酸亚铁锂(Li₂FeSiO₄/C)正极材料。借助X射线衍射、扫描电镜和电化学方法,表征了Mn²⁺、Ti⁴⁺掺杂对Li₂FeSiO₄结构、微观形貌及电化学性能的影响。结果表明:当Mn²⁺取代量x=0～0.15时,充放电比容量逐渐增加,x=0.15时,充放比电容量高达172.9mA·h/g(y=0.05,152.1mAh/g);但当Mn²⁺取代量x=0.20时,充(放)电容量降至118.5mA·h/g(110.9mA·h/g)。Ti⁴⁺掺杂优选条件为Li₂Fe_0.85Mn_0.15SiO₄测试后发现最终合成较优的LiFe_0.80Mn_0.15Ti_0.05SiO₄(y=0.05)首次充(放)电比容量高达178.2mA·h/g(166.7mA·h/g),并且在0.1C倍率下循环20次后容量保持率可达96.4%。

Abstract

The sol-gel method was used to synthesize lithium iron silicate (Li₂FeSiO₄/C) cathode nanocomposite in order to overcome the shortcomings of Li₂FeSiO₄ low conductivity and low lithium ion diffusion rate in the lithium ion battery.The structural,morphological and electrochemical properties of Li₂FeSiO₄/C were characterized by XRD,SEM and electrochemical methods.The results showed that the charge/discharge capacitance increased gradually as increasing the Mn²⁺ substitution concentration x,and the maximum of charge/discharge capacitance was 172.9mAh/g(152.1mAh/g) at x=0.15.When the Mn²⁺ substitution amount x=0.20,the charge/discharge capacitance drop to 118.5mAh/g(110.9mAh/g).For Ti²⁺ doping,the best condition was Li₂Fe_0.85Mn_0.15SiO₄.It was found that LiFe_0.80Mn_0.15Ti_0.05TiO₄(y=0.05) had the maximum charge/discharge capacitance of 178.2mAh/g(166.7mAh/g),and the capacitance retention rate was 96.4% after 20 cycles of 0.1C magnification.

关键词

正极材料 / 离子掺杂 / 溶胶凝胶-微波法 / 电化学性能

Key words

lithium ion battery / codoping / sol-gel method-microwave method / electrochemical performance

引用本文

引用格式 ▾

Mn²⁺、Ti⁴⁺掺杂对Li₂FeSiO₄/C正极材料电化学性能的影响[J]. 化工新型材料, 2019, 47(6): 126-130 DOI:

登录浏览全文

4963

注册一个新账户忘记密码

参考文献

原文顺序 | 出版日期 | 本文引用

[1] 孙彬.五氧化二钒与硫锂离子电池正极材料及其电化学性能研究[D].湘潭:湘潭大学,2016.
[2] 刑玉涛.碳包覆磷酸铁锂正极材料的制备及其电化学性能研究[D].北京:清华大学,2013.
[3] Larsson P,Ahuja R,Nyt6n A.An ab initio study of the Li-ion battery cathode material Li₂FeSiO₄[J].Electrochemistry Communications,2006,8(5):797-800.
[4] Nyten A,Abouimrane A,Armand M.Electrochemical performance of Li₂FeSiO₄ as a new Li-battery cathode material[J].Electrochemistry Communication,2005,7(2):156-160.
[5] Delacourt C,Laffont L,Boucher R,et al.Toward understanding of electrical imitations (electronic,ionic) in LiMPO₄(M=Fe,Mn) electrode materials[J].J Electrochem Soc,2005,152(5):A913-A921.
[6] Nyten A,KAmali S,Haggstrom L,et al.The lithium extraction/insertion mechanism in LiFeSiO[J].Journal of Materials Chemistry,2006,16(23):2266-2272.
[7] Dunn B,Kamath H,Tarascon J M.Electrical energy storage for the grid;a battery of choice[J].Science,2011,334(6058):928.
[8] 吴鹏.我国锂电池及其配套产业发展现状与展望[J].中国高新技术企业,2015(35):3-4.
[9] Shiratsuchi T,Okada S,Doi T,et al.Cathodic performance of LiMn_1-xM_xPO₄ (M=Ti,Mg and Zr) annealed in an inert atmosphere[J].Electrochimica Acta,2009,54(11):3145-3151.
[10] Shin H C,Park S B,Jang H,et al.Rate performance and structural change of Cr-doped LiFePO₄/C during cycling[J].Electrochim Acta,2008,53(27):7946-7951.
[11] Wang S P,Zhou C G,Zhou Q,et al.Preparation of LiFePO₄/C in a reductive atmosphere generated by windward aerobic decomposition of glucose[J].Journal of Power Sources,2011,196(11):5143-5146.
[12] 梁风.孔状纳米级锂离子电池正极材料磷酸铁锂的制备与研究[D].昆明:昆明理工大学,2009.
[13] Song M K,Park S,Alamgir F M,et al.Nanostructured electrodes for lithium ion and lithium-air batteries the latest developments,challenges,and perspectives[J].Materials Science and Engineering R,2011,72(11):220-224.
[14] 燕子鹏,菜舒,周幸,等.正极材料纳米Li₂FeSiO₄/C的溶胶-凝胶法合成及电化学性能[J].硅酸盐学报,2012,40(5):734-738.
[15] Deng C,Zhang S,Yang S Y.Effect of Mn substitution on the structural,morphological and electrochemical behaviors of Li₂Fe_1-xMn_xSiO₄ synthesized via citric acid assisted sol-gel method[J].Journal of Alloys and Compounds,2009,487(1-2):L18-L23.
[16] 胡国荣,曹艳兵,彭忠东,等.微波合成法制备锂离子电池正极材料Li₂FeSiO₄[J].物理化学学报,2009,25(5):1004-1008.
[17] 闫慧,其鲁,张鼎,等.水热法制备锂离子二次电池用球形Li₄Ti₅O₁₂负极材料及其电化学性能[J].无机材料学报,2016,31(11):2-3.
[18] 李云松,傅儒生,程璇,等.前驱体固相法制备硅酸铁锂正极材料[J].硅酸盐学报,2011,39(7):1097-1101.
[19] Shenouda A Y,Liu H K.Electrochemical behaviour of tin borophosphate negative electrodes for energy storage system[J].Journal of Power Sources,2008,185(2):1386-1391.
[20] Shenouda A Y,Liu H K.Studies on electrochemical behaviour of zinc-doped LiFePO₄ for lithium bettery positive electrode[J].Journal of Alloys and Compounds,2009,477(1-2):498-503.
[21] Han D W,Ryu W H,Kim W K,et al.Effects of Li and Cl codoping on the electrochemical performance and structural stability of LiMn₂O₄ cathode materials for hybrid electric vehicle applications[J].Journal of Physical Chemistry C,2013,117(10):4913.