固相法制备钛酸锂电极材料
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摘要
固相法是目前工业化制备钛酸锂电极材料的主要方法。本实验以锐钛型TiO_2、Li_2CO_3为原料,无水乙醇为分散剂,采用球磨辅助固相法合成尖晶石型钛酸锂(Li_4Ti_5O_(12)),并探究原料配比、焙烧温度、焙烧时间对其晶型结构、颗粒形貌及充放电性能的影响。结果表明:在球磨时间为3 h、物料配比n(Li/Ti)(Li与Ti的物质的量比)为0.85、焙烧温度为800℃、焙烧时间为12 h条件下,所得钛酸锂材料的纯度较高、形貌较好,在1C倍率下首次充放电比容量为145.50 mAh/g,100次循环后容量保持率为96.03%,表现出优异的充放电性能。该方法对制备钛酸锂电极材料有一定的指导意义。
The solid phase method is the main method for the industrial preparation of lithium titanate electrode materials. The spinel lithium titanate(Li_4Ti_5O_(12)) was synthesized by ball milling assisted solid phase method with anatase TiO_2 and Li_2CO_3 as raw material and anhydrous ethanol as dispersant. The effects of material ratio, sintering temperature and sintering time on the crystal structure, particle morphology and charge-discharge properties were investigated. The results show that when the milling time is 3 h, the ratio of Li to Ti is 0.85, the calcination temperature is 800 ℃, and the sintering time is 12 h, the purity of lithium titanate is high and the morphology is good. The first charge-discharge capacity of the obtained lithium titanate material is 145.50 mAh/g at 1 C ratio, and the capacity retention rate is 96.03% after 100 cycles, showing excellent charge-discharge performance.It has certain guiding significance for the preparation of lithium titanate electrode material.
The solid phase method is the main method for the industrial preparation of lithium titanate electrode materials. The spinel lithium titanate(Li_4Ti_5O_(12)) was synthesized by ball milling assisted solid phase method with anatase TiO_2 and Li_2CO_3 as raw material and anhydrous ethanol as dispersant. The effects of material ratio, sintering temperature and sintering time on the crystal structure, particle morphology and charge-discharge properties were investigated. The results show that when the milling time is 3 h, the ratio of Li to Ti is 0.85, the calcination temperature is 800 ℃, and the sintering time is 12 h, the purity of lithium titanate is high and the morphology is good. The first charge-discharge capacity of the obtained lithium titanate material is 145.50 mAh/g at 1 C ratio, and the capacity retention rate is 96.03% after 100 cycles, showing excellent charge-discharge performance.It has certain guiding significance for the preparation of lithium titanate electrode material.
引文
1 Yang Zhengdong.Studies on high capacity silicon/carbon composite anodes for lithium-ion batteries.Master’s Thesis,Ningbo Institute of Materials Technology & Enhineering,Chinese Academy of Sciences,China,2016 (in Chinese).杨正东.锂离子电池高容量硅碳复合负极材料复合研究.硕士学位论文,中国科学院宁波材料技术与工程研究所,2016.
2 Cheng Qingtang,Li Hongsen,Shen Laifa,et al.Chinese Journal of Power Sources,2015,39(1),188(in Chinese).成庆堂,李洪森,申来法,等.电源技术,2015,39(1),188.
3 Wang Ling,Gao Pengzhao,Li Dongyun,et al.Journal of the Chinese Ceramic Society,2013,32(1),32(in Chinese).王玲,高朋召,李冬云,等.硅酸盐通报,2013,32(1),32.
4 Hao Y J,Lai Q Y,Liu D Q,et al.Materials Chemistry & Physics,2005,94(2-3),382.
5 Sun B,Wang R,Ni L,et al.Inorganic Chemistry Communications,DOI:10.1016/j.inoche.2018.04.014.
6 Wang L,Wang F,Zhu J,et al.Ceramics International,2018,44(2),1296.
7 Xiang Liangshun,Wang Dingsheng,Gao Mingxia,et al.Journal of Materials Science & Engineering,2011,29(1),46(in Chinese).项良顺,王锭笙,高明霞,等.材料科学与工程学报,2011,29(1),46.
8 Zhang Yaoyao,Wang Dan,Wang Yuanyuan,et al.Rare Metal Materials and Engineering,2014,43(9),2237(in Chinese).张遥遥,王丹,汪元元,等.稀有金属材料与工程,2014,43(9),2237.
9 Talebi-Esfandarani M,Savadogo O.Solid State Ionics,2014,261(4),81.
10 Yan Hui,Qi Lu,Zhang Ding,et al.Journal of Inorganic Materials,2016,31(11),1242(in Chinese).闫慧,其鲁,张鼎,等.无机材料学报,2016,31(11),1242.
11 Mandal D,Jadeja M C,Ghuge N S,et al.Fusion Engineering & Design,2016,112,520.
12 Leonidov I A,Leonidova O N,Perelyaeva L A,et al.Physics of the Solid State,2003,45,2183.
13 Zhao Songhe.Development of lithium titanate as the negative materials for lithium ion batteries.Master’s Thesis,Tianjin University,China,2008 (in Chinese).赵松鹤.锂离子电池负极材料钛酸锂的研究,硕士学位论文,天津大学,2008.
14 Fang Jie,Wang Zhixing,Li Xinhai,et al.The Chinese Joural of Nonferrous Metals,2009,19(12),2179(in Chinese).方杰,王志兴,李新海,等.中国有色金属学报,2009,19(12),2179.
15 Li J,Zhu Y,Wang L,et al.ACS Applied Materials & Interfaces,2014,6(21),18742.
16 Kataoka K,Takahashi Y,Kijima N,et al.Journal of Physics & Chemistry of Solids,2008,69(5),1454.
17 Ning F,He Y B,Li B,et al.Journal of Alloys & Compounds,2012,513,524.
18 Liu Jun,Pan Yi,Zheng Chunman,et al.Materials Review A:Review Papers,2012,26(2),144(in Chinese).刘君,盘毅,郑春满.材料导报:综述篇,2012,26(2),144.
19 Ge Hao.Synthesis and electrochemical performance of spinel lithium titante.Ph.D.Thesis,Harbin Institute of Technology,China,2009 (in Chinese).葛昊.尖晶石型钛酸锂的制备及电化学行为.博士学位论文,哈尔滨工业大学,2009.
20 Wu F,Li X,Wang Z,et al.Nanoscale,2013,5(15),6936.
21 Yang Xiaoyan,Hua Shounan,Zhang Shuyong.Electrochemistry,2000,6(3),350(in Chinese).杨晓燕,华寿南,张树永.电化学,2000,6(3),350.
22 Beuvier T,Richard-Plouet M,Granvalet M L,et al.Inorganic Chemistry,2010,49(18),8457.
23 Marinaro M,Pfanzelt M,Kubiak P,et al.Enginyeria Agroalimentària,2011,28(35),143.
24 Xu J,Jia C,Cao B,et al.Electrochimica Acta,2007,52(28),8044.
25 Liu Wei.Structure and properties analysis of lithium titanate synthesized by hydrothermal method as anode meatrials for lithium-ion batteries.Master’s Thesis,Zhengzhou University,China,2011 (in Chinese).刘微.水热合成锂离子电池负极材料钛酸锂的结构及性能研究.硕士学位论文,郑州大学,2011.
26 Shen K,Chen H,Klaver F,et al.Chemistry of Materials,2014,26(4),1608.
27 Shi Y,Wen L,Li F,et al.Journal of Power Sources,2011,196(20),8610.
28 Shen K,Chen H,Klaver F,et al.Chemistry of Materials,2014,26(4),1608.
29 Shi Y,Wen L,Li F,et al.Journal of Power Sources,2011,196(20),8610.
30 Hu Xuemei,Gu Zhengying,Li Xiaomin,et al.Journal of Inorganic Materials,2015,30(10),1037(in Chinese).虎学梅,顾正莹,李效民,等.无机材料学报,2015,30(10),1037.
31 Shenouda A Y,Murali K R.Journal of Power Sources,2008,176(1),332.
32 Zaghib K,Gauthier M,Brochu F,et al,U.S.patent application,US20120135311,2012.
33 Yi T F,Xie Y,Zhu Y R,et al.Journal of Power Sources,2013,222(2),448.
34 Rahman M M,Wang J Z,Hassan M F,et al.Journal of Power Sources,2010,195(13),4297.
2 Cheng Qingtang,Li Hongsen,Shen Laifa,et al.Chinese Journal of Power Sources,2015,39(1),188(in Chinese).成庆堂,李洪森,申来法,等.电源技术,2015,39(1),188.
3 Wang Ling,Gao Pengzhao,Li Dongyun,et al.Journal of the Chinese Ceramic Society,2013,32(1),32(in Chinese).王玲,高朋召,李冬云,等.硅酸盐通报,2013,32(1),32.
4 Hao Y J,Lai Q Y,Liu D Q,et al.Materials Chemistry & Physics,2005,94(2-3),382.
5 Sun B,Wang R,Ni L,et al.Inorganic Chemistry Communications,DOI:10.1016/j.inoche.2018.04.014.
6 Wang L,Wang F,Zhu J,et al.Ceramics International,2018,44(2),1296.
7 Xiang Liangshun,Wang Dingsheng,Gao Mingxia,et al.Journal of Materials Science & Engineering,2011,29(1),46(in Chinese).项良顺,王锭笙,高明霞,等.材料科学与工程学报,2011,29(1),46.
8 Zhang Yaoyao,Wang Dan,Wang Yuanyuan,et al.Rare Metal Materials and Engineering,2014,43(9),2237(in Chinese).张遥遥,王丹,汪元元,等.稀有金属材料与工程,2014,43(9),2237.
9 Talebi-Esfandarani M,Savadogo O.Solid State Ionics,2014,261(4),81.
10 Yan Hui,Qi Lu,Zhang Ding,et al.Journal of Inorganic Materials,2016,31(11),1242(in Chinese).闫慧,其鲁,张鼎,等.无机材料学报,2016,31(11),1242.
11 Mandal D,Jadeja M C,Ghuge N S,et al.Fusion Engineering & Design,2016,112,520.
12 Leonidov I A,Leonidova O N,Perelyaeva L A,et al.Physics of the Solid State,2003,45,2183.
13 Zhao Songhe.Development of lithium titanate as the negative materials for lithium ion batteries.Master’s Thesis,Tianjin University,China,2008 (in Chinese).赵松鹤.锂离子电池负极材料钛酸锂的研究,硕士学位论文,天津大学,2008.
14 Fang Jie,Wang Zhixing,Li Xinhai,et al.The Chinese Joural of Nonferrous Metals,2009,19(12),2179(in Chinese).方杰,王志兴,李新海,等.中国有色金属学报,2009,19(12),2179.
15 Li J,Zhu Y,Wang L,et al.ACS Applied Materials & Interfaces,2014,6(21),18742.
16 Kataoka K,Takahashi Y,Kijima N,et al.Journal of Physics & Chemistry of Solids,2008,69(5),1454.
17 Ning F,He Y B,Li B,et al.Journal of Alloys & Compounds,2012,513,524.
18 Liu Jun,Pan Yi,Zheng Chunman,et al.Materials Review A:Review Papers,2012,26(2),144(in Chinese).刘君,盘毅,郑春满.材料导报:综述篇,2012,26(2),144.
19 Ge Hao.Synthesis and electrochemical performance of spinel lithium titante.Ph.D.Thesis,Harbin Institute of Technology,China,2009 (in Chinese).葛昊.尖晶石型钛酸锂的制备及电化学行为.博士学位论文,哈尔滨工业大学,2009.
20 Wu F,Li X,Wang Z,et al.Nanoscale,2013,5(15),6936.
21 Yang Xiaoyan,Hua Shounan,Zhang Shuyong.Electrochemistry,2000,6(3),350(in Chinese).杨晓燕,华寿南,张树永.电化学,2000,6(3),350.
22 Beuvier T,Richard-Plouet M,Granvalet M L,et al.Inorganic Chemistry,2010,49(18),8457.
23 Marinaro M,Pfanzelt M,Kubiak P,et al.Enginyeria Agroalimentària,2011,28(35),143.
24 Xu J,Jia C,Cao B,et al.Electrochimica Acta,2007,52(28),8044.
25 Liu Wei.Structure and properties analysis of lithium titanate synthesized by hydrothermal method as anode meatrials for lithium-ion batteries.Master’s Thesis,Zhengzhou University,China,2011 (in Chinese).刘微.水热合成锂离子电池负极材料钛酸锂的结构及性能研究.硕士学位论文,郑州大学,2011.
26 Shen K,Chen H,Klaver F,et al.Chemistry of Materials,2014,26(4),1608.
27 Shi Y,Wen L,Li F,et al.Journal of Power Sources,2011,196(20),8610.
28 Shen K,Chen H,Klaver F,et al.Chemistry of Materials,2014,26(4),1608.
29 Shi Y,Wen L,Li F,et al.Journal of Power Sources,2011,196(20),8610.
30 Hu Xuemei,Gu Zhengying,Li Xiaomin,et al.Journal of Inorganic Materials,2015,30(10),1037(in Chinese).虎学梅,顾正莹,李效民,等.无机材料学报,2015,30(10),1037.
31 Shenouda A Y,Murali K R.Journal of Power Sources,2008,176(1),332.
32 Zaghib K,Gauthier M,Brochu F,et al,U.S.patent application,US20120135311,2012.
33 Yi T F,Xie Y,Zhu Y R,et al.Journal of Power Sources,2013,222(2),448.
34 Rahman M M,Wang J Z,Hassan M F,et al.Journal of Power Sources,2010,195(13),4297.