离子液体作为电解液添加剂用于高压锂离子电池
|
摘要
合成了功能化离子液体1-丁基-3-甲基咪唑双(三氟甲磺酰)亚胺盐(BMIMTFSI)作为高压锂离子电池电解液添加剂,用于抑制有机溶剂的氧化,以提高碳酸酯类电解液的耐高压性。分别采用充放电测试、电化学交流阻抗(EIS)、循环伏安法(CV)和扫描电子显微镜(SEM)等研究了LiNi_(0.5)Mn_(1.5)O_4/Li电池的电化学行为和LiNi_(0.5)Mn_(1.5)O_4材料表面形貌。结果表明,当在电解液中添加20%(体积分数) BMIMTFSI时,LiNi_(0.5)Mn_(1.5)O_4/Li电池在室温、0.2C下的最高放电比容量是126.81 mA·h·g~(-1),5C下的放电比容量为109.36 mA·h·g~(-1),比在1 mol·L~(-1)LiPF_6-EC/DMC电解液中的放电比容量提高了91.7%;且该电池在0.2C下循环50圈后的放电比容量保持率在95%左右,比用碳酸酯类电解液提高了近10%。SEM结果表明,在碳酸酯类电解液中加入BMIMTFSI后,LiNi_(0.5)Mn_(1.5)O_4电极表面附着了一层均匀且致密的固态电解质界面(SEI)膜。
The functionalized ionic liquids 1-butyl-3-methylimidazoliumbis(trifluoromethanesulfonyl)imide(BMIMTFSI) was synthesized as a high-pressure lithium ion battery electrolyte additive for inhibiting the oxidation of organic solvents to enhance carbonic acid. The electrochemical behaviors of LiNi_(0.5)Mn_(1.5)O_4/Li batteries and the surface morphology of LiNi_(0.5)Mn_(1.5)O_4 electrode were studied by charge-discharge test, electrochemical impedance spectroscopy(EIS), cyclic voltammetry(CV) and scanning electron microscopy(SEM). The results show that when 20%(vol) BMIMTFSI is added to carbonate-based electrolyte, the highest discharge capacity of LiNi_(0.5)Mn_(1.5)O_4/Li cells is 126.81 mA·h·g~(-1) at 0.2 C rate, and the discharge capacity is 109.36 mA·h·g~(-1) at high rate of 5 C, which is 91.7% higher than that in 1.0 mol·L~(-1)LiPF_6-EC/DMC electrolyte. And the discharge capacity retention rate of LiNi_(0.5)Mn_(1.5)O_4/Li cells reaches about 95% after 50 cycles at 0.2 C rate, which is nearly 10% higher than that with blank electrolytes. The results of SEM showed that a uniform and compact solid electrolyte interface(SEI) film was attached to the surface of LiNi_(0.5)Mn_(1.5)O_4 electrode after adding BMIMTFSI to carbonate-based electrolyte.
The functionalized ionic liquids 1-butyl-3-methylimidazoliumbis(trifluoromethanesulfonyl)imide(BMIMTFSI) was synthesized as a high-pressure lithium ion battery electrolyte additive for inhibiting the oxidation of organic solvents to enhance carbonic acid. The electrochemical behaviors of LiNi_(0.5)Mn_(1.5)O_4/Li batteries and the surface morphology of LiNi_(0.5)Mn_(1.5)O_4 electrode were studied by charge-discharge test, electrochemical impedance spectroscopy(EIS), cyclic voltammetry(CV) and scanning electron microscopy(SEM). The results show that when 20%(vol) BMIMTFSI is added to carbonate-based electrolyte, the highest discharge capacity of LiNi_(0.5)Mn_(1.5)O_4/Li cells is 126.81 mA·h·g~(-1) at 0.2 C rate, and the discharge capacity is 109.36 mA·h·g~(-1) at high rate of 5 C, which is 91.7% higher than that in 1.0 mol·L~(-1)LiPF_6-EC/DMC electrolyte. And the discharge capacity retention rate of LiNi_(0.5)Mn_(1.5)O_4/Li cells reaches about 95% after 50 cycles at 0.2 C rate, which is nearly 10% higher than that with blank electrolytes. The results of SEM showed that a uniform and compact solid electrolyte interface(SEI) film was attached to the surface of LiNi_(0.5)Mn_(1.5)O_4 electrode after adding BMIMTFSI to carbonate-based electrolyte.
引文
[1] Sato T, Maruo T, Marukane S, et al. Ionic liquids containing carbonate solvent as electrolytes for lithium ion cells[J]. Journal of Power Sources, 2004, 138(1):253-261.
[2] Goodenough J B. Rechargeable batteries:challenges old and new[J]. Journal of Solid State Electrochemistry, 2012, 16(6):2019-2029.
[3] Tarascon J M, Armand M. Issues and challenges facing rechargeable lithium batteries[J]. Nature, 2001, 414(6861):359-367.
[4] Choi N S, Chen Z H, Freunberger S A, et al. Challenges facing lithium batteries and electrical double-layer capacitors[J]. Angew.Chem. Int. Ed. Engl., 2012, 51(40):9994-10024.
[5] Goodenough J B, Park K S. The Li-ion rechargeable battery:a perspective[J]. Journal of the American Chemical Society, 2013,135(4):1167-1176.
[6] Fang X, Ding N, Feng X Y, et al. Study of LiNi0.5Mn1.5O4synthesized via a chloride-ammonia co-precipitation method:electrochemical performance, diffusion coefficient and capacity loss mechanism[J]. Electrochimica Acta, 2009, 54(28):7471-7475.
[7] Kim J H, Myung S T, Sun Y K. Molten salt synthesis of LiNi0.5Mn1.5O4spinel for 5 V class cathode material of Li-ion secondary battery[J]. Electrochimica Acta, 2004, 49(2):219-227.
[8] Park S H, Sun Y K. Synthesis and electrochemical properties of 5V spinel LiNi0.5Mn1.5O4cathode materials prepared by ultrasonic spray pyrolysis method[J]. Electrochimica Acta, 2004, 50(2):431-434.
[9] Wang Z N, Cai Y J, Wang Z H, et al. Vinyl-functionalized imidazolium ionic liquids as new electrolyte additives for highvoltage Li-ion batteries[J]. Journal of Solid State Electrochemistry, 2013, 17(11):2839-2848.
[10] Arrebola J C, Caballero A, Hernán L, et al. A high energy Li-ion battery based on nanosized LiNi0.5Mn1.5O4cathode material[J].Journal of Power Sources, 2008, 183(1):310-315.
[11] Talyosef Y, Markovsky B, Salitra G, et al. The study of LiNi0.5Mn1.5O45 V cathodes for Li-ion batteries[J]. Journal of Power Sources, 2005, 146(1):664-669.
[12] Zhang L L, Ma Y L, Du C Y, et al. Research on the high-voltage electrolyte for lithium ion batteries[J]. Progress in Chemistry,2014, 26(4):553-559.
[13] Sun Y K, Hong K J, Prakash J, et al. Electrochemical performance of nano-sized ZnO-coated LiNi0.5Mn1.5O4spinel as 5 V materials at elevated temperatures[J]. Electrochemistry Communications,2002, 4(4):344-348.
[14] Chen J H, Zhang H, Wang M L, et al. Improving the electrochemical performance of high voltage spinel cathode at elevated temperature by a novel electrolyte additive[J]. Journal of Power Sources, 2016, 303:41-48.
[15] Aurbach D, Markovsky B, Salitra G, et al. Review on electrodeelectrolyte solution interactions, related to cathode materials for Li-ion batteries[J]. Journal of Power Sources, 2007, 165(2):491-499.
[16]李放放,陈仕谋.高压锂离子电池电解液添加剂研究进展[J].储能科学与技术, 2016, 5(4):436-441.Li F F, Chen S M. Research progress on electrolyte additives for high voltage lithium-ion batteries[J]. Energy Storage Science and Technology, 2016, 5(4):436-441.
[17]何新快,侯柏龙,吴璐烨,等.咪唑类离子液体电化学窗口影响因素的研究进展[J].化工新型材料, 2014, 42(6):35-38.He X K, Hou B L, Wu L Y, et al. Effect factors of electrochemical windows of imidazolium ionic liquids[J]. New Chemical Materials,2014, 42(6):35-38.
[18]王力臻,孙新科,杨许召,等.离子液体在锂离子电池中的应用研究进展[J].电池工业, 2012, 17(3):165-170.Wang L Z, Sun X K, Yang X Z, et al. Application and development of ionic liquids in Li-ion batteries[J]. Chinese Battery Industry, 2012, 17(3):165-170.
[19]刘卉,陶国宏,邵元华,等.功能化的离子液体在电化学中的应用[J].化学通报, 2004, 11:795-801.Liu H, Tao G H, Shao Y H, et al. Applications of functionalized ionic liquids in electrochemistry[J]. Chemistry, 2004, 11:795-801.
[20] Zhang W, Li Y, Lin C X, et al. Electrochemical polymerization of imidazolum‐ionic liquids bearing a pyrrole moiety[J]. Journal of Polymer Science Part A Polymer Chemistry, 2008, 46(12):4151-4161.
[21] Green M D, Cruz D S D L, Ye Y S, et al. Alkyl‐substituted N‐vinylimidazolium polymerized ionic liquids:thermal properties and ionic conductivities[J]. Macromolecular Chemistry&Physics,2011, 212(23):2522-2528.
[22] Zhou Z B, Matsumoto H, Tatsumi K. Low-melting, low-viscous,hydrophobic ionic liquids:aliphatic quaternary ammonium salts with perfluoroalkyltrifluoroborates[J]. Chem. Eur. J., 2010, 11(2):752-766.
[23] Tsunashima K, Sugiya M. Physical and electrochemical properties of low-viscosity phosphonium ionic liquids as potential electrolytes[J]. Electrochemistry Communications, 2007, 9(9):2353-2358.
[24] Matsumoto H, Sakaebe H, Tatsumi K. Preparation of room temperature ionic liquids based on aliphatic onium cations and asymmetric amide anions and their electrochemical properties as a lithium battery electrolyte[J]. Journal of Power Sources, 2005,146(1):45-50.
[25] McEwen A B, Ngo H L, LeCompte K, et al. Electrochemical properties of imidazolium salt electrolytes for electrochemical capacitor applications[J]. Journal of the Electrochemical Society,1999, 146(5):1687-1695.
[26]曹宇,姚田,何志坚,等.离子液体物化性质的理论研究方法及进展[C]//2012年中国药学大会暨第十二届中国药师周论文集.南京:中国药学会, 2012:121-122.Cao Y, Yao T, He Z J, et al. The theoretical research and progress on physical chemistry properties of ionic liquids[C]//2012 Chinese Pharmacology Conference and the 12th Chinese Pharmacist's Weekly Collection. Nanjing:Chinese Pharmaceutical Association,2012:121-122.
[27] Xing L D, Wang C Y, Xu M Q, et al. Theoretical study on reduction mechanism of 1,3-benzodioxol-2-one for the formation of solid electrolyte interface on anode of lithium ion battery[J].Journal of Power Sources, 2009, 189(1):689-692.
[28]王赟,杨亮,高丹. 1-丁基-3-甲基咪唑四氟硼酸盐的合成研究[J].广东化工, 2011, 38(9):8-9.Wang Y, Yang L, Gao D. The study on the synthesis of 1-butyl-3-methylimidazolium tetrafluoroborate[J]. Guangdong Chemical Industry, 2011, 38(9):8-9.
[29] Hikari S, Hajime M. N-methyl-N-propylpiperidinium bis(trifluoromethanesulfonyl)imide(PP13-TFSI)-novel electrolyte base for Li battery[J]. Electrochemistry Communications, 2003, 5(7):594-598.
[30]郑丽丽,郭晨,刘会洲.离子液体的红外光谱研究[J].光谱学与光谱分析, 2006, 26(7):33-34.Zheng L L, Guo C, Liu H Z. The FT-IR study of ionic liquids[J].Spectroscopy and Spectral Analysis, 2006, 26(7):33-34.
[31] Han Y K, Lee K, Jung S C, et al. Computational screening of solid electrolyte interphase forming additives in lithium-ion batteries[J]. Computational and Theoretical Chemistry, 2014, 1031:64-68.
[32]谢晓华,陈立宝,高阳,等.锂离子电池电解液功能组分的设计[J].电池, 2006, 36(6):435-437.Xie X H, Chen L B, Gao Y, et al. Design of electrolyte functional components for Li-ion battery[J]. Battery Bimonthly, 2006, 36(6):435-437.
[33] Halls M D, Tasaki K. High-throughput quantum chemistry and virtual screening for lithium ion battery electrolyte additives[J].Journal of Power Sources, 2010, 195(5):1472-1478.
[2] Goodenough J B. Rechargeable batteries:challenges old and new[J]. Journal of Solid State Electrochemistry, 2012, 16(6):2019-2029.
[3] Tarascon J M, Armand M. Issues and challenges facing rechargeable lithium batteries[J]. Nature, 2001, 414(6861):359-367.
[4] Choi N S, Chen Z H, Freunberger S A, et al. Challenges facing lithium batteries and electrical double-layer capacitors[J]. Angew.Chem. Int. Ed. Engl., 2012, 51(40):9994-10024.
[5] Goodenough J B, Park K S. The Li-ion rechargeable battery:a perspective[J]. Journal of the American Chemical Society, 2013,135(4):1167-1176.
[6] Fang X, Ding N, Feng X Y, et al. Study of LiNi0.5Mn1.5O4synthesized via a chloride-ammonia co-precipitation method:electrochemical performance, diffusion coefficient and capacity loss mechanism[J]. Electrochimica Acta, 2009, 54(28):7471-7475.
[7] Kim J H, Myung S T, Sun Y K. Molten salt synthesis of LiNi0.5Mn1.5O4spinel for 5 V class cathode material of Li-ion secondary battery[J]. Electrochimica Acta, 2004, 49(2):219-227.
[8] Park S H, Sun Y K. Synthesis and electrochemical properties of 5V spinel LiNi0.5Mn1.5O4cathode materials prepared by ultrasonic spray pyrolysis method[J]. Electrochimica Acta, 2004, 50(2):431-434.
[9] Wang Z N, Cai Y J, Wang Z H, et al. Vinyl-functionalized imidazolium ionic liquids as new electrolyte additives for highvoltage Li-ion batteries[J]. Journal of Solid State Electrochemistry, 2013, 17(11):2839-2848.
[10] Arrebola J C, Caballero A, Hernán L, et al. A high energy Li-ion battery based on nanosized LiNi0.5Mn1.5O4cathode material[J].Journal of Power Sources, 2008, 183(1):310-315.
[11] Talyosef Y, Markovsky B, Salitra G, et al. The study of LiNi0.5Mn1.5O45 V cathodes for Li-ion batteries[J]. Journal of Power Sources, 2005, 146(1):664-669.
[12] Zhang L L, Ma Y L, Du C Y, et al. Research on the high-voltage electrolyte for lithium ion batteries[J]. Progress in Chemistry,2014, 26(4):553-559.
[13] Sun Y K, Hong K J, Prakash J, et al. Electrochemical performance of nano-sized ZnO-coated LiNi0.5Mn1.5O4spinel as 5 V materials at elevated temperatures[J]. Electrochemistry Communications,2002, 4(4):344-348.
[14] Chen J H, Zhang H, Wang M L, et al. Improving the electrochemical performance of high voltage spinel cathode at elevated temperature by a novel electrolyte additive[J]. Journal of Power Sources, 2016, 303:41-48.
[15] Aurbach D, Markovsky B, Salitra G, et al. Review on electrodeelectrolyte solution interactions, related to cathode materials for Li-ion batteries[J]. Journal of Power Sources, 2007, 165(2):491-499.
[16]李放放,陈仕谋.高压锂离子电池电解液添加剂研究进展[J].储能科学与技术, 2016, 5(4):436-441.Li F F, Chen S M. Research progress on electrolyte additives for high voltage lithium-ion batteries[J]. Energy Storage Science and Technology, 2016, 5(4):436-441.
[17]何新快,侯柏龙,吴璐烨,等.咪唑类离子液体电化学窗口影响因素的研究进展[J].化工新型材料, 2014, 42(6):35-38.He X K, Hou B L, Wu L Y, et al. Effect factors of electrochemical windows of imidazolium ionic liquids[J]. New Chemical Materials,2014, 42(6):35-38.
[18]王力臻,孙新科,杨许召,等.离子液体在锂离子电池中的应用研究进展[J].电池工业, 2012, 17(3):165-170.Wang L Z, Sun X K, Yang X Z, et al. Application and development of ionic liquids in Li-ion batteries[J]. Chinese Battery Industry, 2012, 17(3):165-170.
[19]刘卉,陶国宏,邵元华,等.功能化的离子液体在电化学中的应用[J].化学通报, 2004, 11:795-801.Liu H, Tao G H, Shao Y H, et al. Applications of functionalized ionic liquids in electrochemistry[J]. Chemistry, 2004, 11:795-801.
[20] Zhang W, Li Y, Lin C X, et al. Electrochemical polymerization of imidazolum‐ionic liquids bearing a pyrrole moiety[J]. Journal of Polymer Science Part A Polymer Chemistry, 2008, 46(12):4151-4161.
[21] Green M D, Cruz D S D L, Ye Y S, et al. Alkyl‐substituted N‐vinylimidazolium polymerized ionic liquids:thermal properties and ionic conductivities[J]. Macromolecular Chemistry&Physics,2011, 212(23):2522-2528.
[22] Zhou Z B, Matsumoto H, Tatsumi K. Low-melting, low-viscous,hydrophobic ionic liquids:aliphatic quaternary ammonium salts with perfluoroalkyltrifluoroborates[J]. Chem. Eur. J., 2010, 11(2):752-766.
[23] Tsunashima K, Sugiya M. Physical and electrochemical properties of low-viscosity phosphonium ionic liquids as potential electrolytes[J]. Electrochemistry Communications, 2007, 9(9):2353-2358.
[24] Matsumoto H, Sakaebe H, Tatsumi K. Preparation of room temperature ionic liquids based on aliphatic onium cations and asymmetric amide anions and their electrochemical properties as a lithium battery electrolyte[J]. Journal of Power Sources, 2005,146(1):45-50.
[25] McEwen A B, Ngo H L, LeCompte K, et al. Electrochemical properties of imidazolium salt electrolytes for electrochemical capacitor applications[J]. Journal of the Electrochemical Society,1999, 146(5):1687-1695.
[26]曹宇,姚田,何志坚,等.离子液体物化性质的理论研究方法及进展[C]//2012年中国药学大会暨第十二届中国药师周论文集.南京:中国药学会, 2012:121-122.Cao Y, Yao T, He Z J, et al. The theoretical research and progress on physical chemistry properties of ionic liquids[C]//2012 Chinese Pharmacology Conference and the 12th Chinese Pharmacist's Weekly Collection. Nanjing:Chinese Pharmaceutical Association,2012:121-122.
[27] Xing L D, Wang C Y, Xu M Q, et al. Theoretical study on reduction mechanism of 1,3-benzodioxol-2-one for the formation of solid electrolyte interface on anode of lithium ion battery[J].Journal of Power Sources, 2009, 189(1):689-692.
[28]王赟,杨亮,高丹. 1-丁基-3-甲基咪唑四氟硼酸盐的合成研究[J].广东化工, 2011, 38(9):8-9.Wang Y, Yang L, Gao D. The study on the synthesis of 1-butyl-3-methylimidazolium tetrafluoroborate[J]. Guangdong Chemical Industry, 2011, 38(9):8-9.
[29] Hikari S, Hajime M. N-methyl-N-propylpiperidinium bis(trifluoromethanesulfonyl)imide(PP13-TFSI)-novel electrolyte base for Li battery[J]. Electrochemistry Communications, 2003, 5(7):594-598.
[30]郑丽丽,郭晨,刘会洲.离子液体的红外光谱研究[J].光谱学与光谱分析, 2006, 26(7):33-34.Zheng L L, Guo C, Liu H Z. The FT-IR study of ionic liquids[J].Spectroscopy and Spectral Analysis, 2006, 26(7):33-34.
[31] Han Y K, Lee K, Jung S C, et al. Computational screening of solid electrolyte interphase forming additives in lithium-ion batteries[J]. Computational and Theoretical Chemistry, 2014, 1031:64-68.
[32]谢晓华,陈立宝,高阳,等.锂离子电池电解液功能组分的设计[J].电池, 2006, 36(6):435-437.Xie X H, Chen L B, Gao Y, et al. Design of electrolyte functional components for Li-ion battery[J]. Battery Bimonthly, 2006, 36(6):435-437.
[33] Halls M D, Tasaki K. High-throughput quantum chemistry and virtual screening for lithium ion battery electrolyte additives[J].Journal of Power Sources, 2010, 195(5):1472-1478.