聚合物基PTC导电材料的制备及其在锂离子电池中的应用
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摘要
锂离子电池内短路是诱发电池热失控的主要原因,适当的安全性添加剂可以阻止电池热失控的发生。本文通过界面聚合法在聚乙烯蜡表面生成适量的导电聚苯胺,制备了一种具有良好导电性能的PTC材料(PANI-PEW),并对PANI-PEW的微观形貌、电导率以及添加至LiFePO_4正极中的电化学性能进行了对比分析。测试结果表明,PANI-PEW在常温下的电导率为1.08×10~(-3)S/m,在90～120℃时,其电阻值急剧增大。在0.5 C和1 C倍率下,PANI-PEW的加入对LiFePO_4电池的阻抗和循环性能影响较小,而经过120℃热处理后的含15%(质量分数)PANI-PEW的极片,其电池的阻抗大幅增加且首次放电比容量只有35.3 mA·h/g,在第12次循环后,放电比容量接近于0。以上结果表明,PANI-PEW是一种性能优异的PTC材料且能在120℃时阻止电池热失控的发生。
Short circuit in lithium ion battery is the main cause of thermal runaway, the proper safety additives can prevent the thermal runaway. A positive temperature coefficient material(PANI-PEW)was prepared by polymering amount of PANI particles on the surface of PEW. The morphology and conductivity of PANI-PEW, the electrochemical performance of LiFePO_4 batteries with PANI-PEW were tested at room temperature and 120 ℃. The results showed as follow: the conductivity of PANIPEW was 1.08×10~(-3) S/m at room temperature and its resistant increased rapidly during 90～120 ℃. It had little effect on the impedance and cycling performance when PANI-PEW introduced into LiFePO_4 battery at 0.5 C and 1 C. But the impedance of LiFePO_4 battery with 15% PANI-PEW increased rapidly and the first specific capacity only was 35.3 mA·h/g after the LiFePO_4 electrode with 15% PANI-PEW was treated at 120 ℃ for 1 min, even after the 12 th cycle, the specific capacity closed to 0. This study indicate that the PANI-PEW is an excellent PTC composite and improved the safety performance of LiFePO_4 battery at 120 ℃.
Short circuit in lithium ion battery is the main cause of thermal runaway, the proper safety additives can prevent the thermal runaway. A positive temperature coefficient material(PANI-PEW)was prepared by polymering amount of PANI particles on the surface of PEW. The morphology and conductivity of PANI-PEW, the electrochemical performance of LiFePO_4 batteries with PANI-PEW were tested at room temperature and 120 ℃. The results showed as follow: the conductivity of PANIPEW was 1.08×10~(-3) S/m at room temperature and its resistant increased rapidly during 90～120 ℃. It had little effect on the impedance and cycling performance when PANI-PEW introduced into LiFePO_4 battery at 0.5 C and 1 C. But the impedance of LiFePO_4 battery with 15% PANI-PEW increased rapidly and the first specific capacity only was 35.3 mA·h/g after the LiFePO_4 electrode with 15% PANI-PEW was treated at 120 ℃ for 1 min, even after the 12 th cycle, the specific capacity closed to 0. This study indicate that the PANI-PEW is an excellent PTC composite and improved the safety performance of LiFePO_4 battery at 120 ℃.
引文
[1]BANDHAUER T M,GARIMELLA S,FULLER T F.A critical review of thermal issues in lithium-ion batteries[J].Journal of the Electrochemical Society,2011,158(3):R1-R25.
[2]刘力硕,张明轩,卢兰光,等.锂离子电池内短路机理与检测研究进展[J].储能科学与技术,2018,7(6):1003-1015.LIU Lishuo,ZHANG Mmingxuan,LU Languang,et al.Recent progress on mechanism and detection of internal short circuit in lithium-ion batteries[J].Energy Storage Science and Technology,2018,7(6):1003-1015.
[3]VELUCHAMY A,DOH C H,KIM D H,et al.Thermal analysis of LixCoO2 cathode material of lithium ion battery[J].Journal of Power Sources,2009,189(1):855-858.
[4]SMITH K,KIM G H,DARCY E,et al.Thermal/electrical modeling for abuse-tolerant design of lithium ion modules[J].International Journal of Energy Research,2010,34(2):204-215.
[5]BAGINSKA M,BLAISZIK B J,MERRIMAN R J,et al.Autonomic shutdown of lithium‐ion batteries using thermoresponsive microspheres[J].Advanced Energy Materials,2012,2(5):583-590.
[6]FENG X M,AI X P,YANG H X.A positive-temperature-coefficient electrode with thermal cut-off mechanism for use in rechargeable lithium batteries[J].Electrochemistry Communications,2004,6(10):1021-1024.
[7]JI W,WANG F,LIU D,et al.Building thermally stable Li-ion batteries using a temperature-responsive cathode[J].Journal of Materials Chemistry A,2016,4(29):11239-11246.
[8]XIA L,LI S L,AI X P,et al.Temperature-sensitive cathode materials for safer lithium-ion batteries[J].Energy&Environmental Science,2011,4(8):2845-2848.
[9]KISE M,YOSHIOKA S,HAMANO K,et al.Alternating current impedance behavior and overcharge tolerance of lithium-ion batteries using positive temperature coefficient cathodes[J].Journal of The Electrochemical Society,2006,153(6):A1004-A1011.
[10]KISE M,YOSHIOKA S,KURIKI H.Relation between composition of the positive electrode and cell performance and safety of lithium-ion PTC batteries[J].Journal of Power Sources,2007,174(2):861-866.
[11]ZHONG H,KONG C,ZHAN H,et al.Safe positive temperature coefficient composite cathode for lithium ion battery[J].Journal of Power Sources,2012,216:273-280.
[12]李惠,吉维肖,曹余良,等.锂离子电池热失控防范技术[J].储能科学与技术,2018,7(3):376-383.LI Hui,JI Weixiao,CAO Yuliang,et al.Thermal runaway-preventing technologies for lithium-ion batteries[J].Energy Storage Science and Technology,2018,7(3):376-383.
[13]吴迪.聚乙烯蜡的亲水改性及乳化研究[D].长春:长春工业大学,2018.WU Di.Study on the hydrophilic modification of polyethylene wax and it's emulsification[D].Changchun:Changchun University of Technology,2018.
[14]张幸珂,曹祖宾,韩冬云,等.聚乙烯副产物聚乙烯蜡的热解及轻质馏分的GC-MS分析[J].化工环保,2018,38(3):358-362.ZHANG Xingke,CAO Zubing,HAN Dongyun,et al.Pyrolysis of polyethylene by-product polyethylene wax and GC-MS analysis of light fraction[J].Environmental Protection of Chemical Industry,2018,38(3):358-362.
[15]王素敏,李璐,王奇观,等.水性共价连接型聚苯胺/碳纳米管复合材料的制备及电学性能[J].合成材料老化与应用,2018,47(2):37-41.WANG Sumin,LI Lu,WANG Qiguan,et al.Preparation and conductivity of the water-borne covalently-linked polyaniline/carbon nanotube composite[J].Synthetic Materials Aging and Application,2018,47(2):37-41.
[16]SILAKHORI M,NAGHAVI M S,METSELAAR H S C,et al.Accelerated thermal cycling test of microencapsulated paraffin wax/polyaniline made by simple preparation method for solar thermal energy storage[J].Materials,2013,6(5):1608-1620.
[17]王香琴,辛斌杰,许鉴.导电聚苯胺的制备及其表征[J].材料导报,2013,27(16):86-90.WA N G X i a n g q i n,X I N B i n g j i e,X U J i a n.S y n t h e s i s a n d Characterization of Polyaniline Membrane[J].Materials Reports,2013,27(16):86-90.
[18]XU X,XIAO H,GUAN Y,et al.Permanent antistatic polypropylene based on polyethylene wax/polypropylene wax grafting sodium acrylate[J].Journal of Applied Polymer Science,2012,126(1):83-90.
[19]钱龙,饶睦敏,朱丹,等.阻燃剂在锂离子电池中的应用[J].电池,2015,45(6):319-321.QIAN Long,RAO Mumin,ZHU Dan,et al.The application of flame retardants in Li-ion battery[J].Battery Bimonthly,2015,45(6):319-321.
[20]张世明,车海英,杨柯,等.基于LiFePO4和活性炭的混合型电化学储能器件研究[J].储能科学与技术,2018,7(2):240-247.ZHANG Shiming,CHE Haiying,YANG Ke,et al.Development of hybrid electrochemical energy storage device based on LiFePO4 and activated carbon[J].Energy Storage Science and Technology,2018,7(2):240-247.
[21]PARK C K,RUBINO R.Thermally stable electrolyte for lithium-ion batteries[J].ECS Transactions,2014,58(26):1-9.
[22]景燕,刘亚飞,陈彦彬.锂电正极材料开发用纽扣电池测试技术研究[J].广东化工,2017,44(18):55-56+41.JING Yan,LIU Yafei,CHEN Yanbing.Research on the technology of the coin cell test for lithium-ion battery cathode materials[J].Guangdong Chemical Industry,2017,44(18):55-56+41.
[2]刘力硕,张明轩,卢兰光,等.锂离子电池内短路机理与检测研究进展[J].储能科学与技术,2018,7(6):1003-1015.LIU Lishuo,ZHANG Mmingxuan,LU Languang,et al.Recent progress on mechanism and detection of internal short circuit in lithium-ion batteries[J].Energy Storage Science and Technology,2018,7(6):1003-1015.
[3]VELUCHAMY A,DOH C H,KIM D H,et al.Thermal analysis of LixCoO2 cathode material of lithium ion battery[J].Journal of Power Sources,2009,189(1):855-858.
[4]SMITH K,KIM G H,DARCY E,et al.Thermal/electrical modeling for abuse-tolerant design of lithium ion modules[J].International Journal of Energy Research,2010,34(2):204-215.
[5]BAGINSKA M,BLAISZIK B J,MERRIMAN R J,et al.Autonomic shutdown of lithium‐ion batteries using thermoresponsive microspheres[J].Advanced Energy Materials,2012,2(5):583-590.
[6]FENG X M,AI X P,YANG H X.A positive-temperature-coefficient electrode with thermal cut-off mechanism for use in rechargeable lithium batteries[J].Electrochemistry Communications,2004,6(10):1021-1024.
[7]JI W,WANG F,LIU D,et al.Building thermally stable Li-ion batteries using a temperature-responsive cathode[J].Journal of Materials Chemistry A,2016,4(29):11239-11246.
[8]XIA L,LI S L,AI X P,et al.Temperature-sensitive cathode materials for safer lithium-ion batteries[J].Energy&Environmental Science,2011,4(8):2845-2848.
[9]KISE M,YOSHIOKA S,HAMANO K,et al.Alternating current impedance behavior and overcharge tolerance of lithium-ion batteries using positive temperature coefficient cathodes[J].Journal of The Electrochemical Society,2006,153(6):A1004-A1011.
[10]KISE M,YOSHIOKA S,KURIKI H.Relation between composition of the positive electrode and cell performance and safety of lithium-ion PTC batteries[J].Journal of Power Sources,2007,174(2):861-866.
[11]ZHONG H,KONG C,ZHAN H,et al.Safe positive temperature coefficient composite cathode for lithium ion battery[J].Journal of Power Sources,2012,216:273-280.
[12]李惠,吉维肖,曹余良,等.锂离子电池热失控防范技术[J].储能科学与技术,2018,7(3):376-383.LI Hui,JI Weixiao,CAO Yuliang,et al.Thermal runaway-preventing technologies for lithium-ion batteries[J].Energy Storage Science and Technology,2018,7(3):376-383.
[13]吴迪.聚乙烯蜡的亲水改性及乳化研究[D].长春:长春工业大学,2018.WU Di.Study on the hydrophilic modification of polyethylene wax and it's emulsification[D].Changchun:Changchun University of Technology,2018.
[14]张幸珂,曹祖宾,韩冬云,等.聚乙烯副产物聚乙烯蜡的热解及轻质馏分的GC-MS分析[J].化工环保,2018,38(3):358-362.ZHANG Xingke,CAO Zubing,HAN Dongyun,et al.Pyrolysis of polyethylene by-product polyethylene wax and GC-MS analysis of light fraction[J].Environmental Protection of Chemical Industry,2018,38(3):358-362.
[15]王素敏,李璐,王奇观,等.水性共价连接型聚苯胺/碳纳米管复合材料的制备及电学性能[J].合成材料老化与应用,2018,47(2):37-41.WANG Sumin,LI Lu,WANG Qiguan,et al.Preparation and conductivity of the water-borne covalently-linked polyaniline/carbon nanotube composite[J].Synthetic Materials Aging and Application,2018,47(2):37-41.
[16]SILAKHORI M,NAGHAVI M S,METSELAAR H S C,et al.Accelerated thermal cycling test of microencapsulated paraffin wax/polyaniline made by simple preparation method for solar thermal energy storage[J].Materials,2013,6(5):1608-1620.
[17]王香琴,辛斌杰,许鉴.导电聚苯胺的制备及其表征[J].材料导报,2013,27(16):86-90.WA N G X i a n g q i n,X I N B i n g j i e,X U J i a n.S y n t h e s i s a n d Characterization of Polyaniline Membrane[J].Materials Reports,2013,27(16):86-90.
[18]XU X,XIAO H,GUAN Y,et al.Permanent antistatic polypropylene based on polyethylene wax/polypropylene wax grafting sodium acrylate[J].Journal of Applied Polymer Science,2012,126(1):83-90.
[19]钱龙,饶睦敏,朱丹,等.阻燃剂在锂离子电池中的应用[J].电池,2015,45(6):319-321.QIAN Long,RAO Mumin,ZHU Dan,et al.The application of flame retardants in Li-ion battery[J].Battery Bimonthly,2015,45(6):319-321.
[20]张世明,车海英,杨柯,等.基于LiFePO4和活性炭的混合型电化学储能器件研究[J].储能科学与技术,2018,7(2):240-247.ZHANG Shiming,CHE Haiying,YANG Ke,et al.Development of hybrid electrochemical energy storage device based on LiFePO4 and activated carbon[J].Energy Storage Science and Technology,2018,7(2):240-247.
[21]PARK C K,RUBINO R.Thermally stable electrolyte for lithium-ion batteries[J].ECS Transactions,2014,58(26):1-9.
[22]景燕,刘亚飞,陈彦彬.锂电正极材料开发用纽扣电池测试技术研究[J].广东化工,2017,44(18):55-56+41.JING Yan,LIU Yafei,CHEN Yanbing.Research on the technology of the coin cell test for lithium-ion battery cathode materials[J].Guangdong Chemical Industry,2017,44(18):55-56+41.