Li_2MnO_3正极材料中掺杂Co、Ni的电化学性能研究
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摘要
分别以金属Co和Ni替代Li_2MnO_3中的部分Mn,并采用高温固相合成法制备Li_2Mn_(0.5)Ni_(0.5)O_3和Li_2Mn_(0.5)Co_(0.5)O_3正极材料,通过SEM分析和X射线衍射观察材料的微观形貌和晶体结构,循环伏安法、交流阻抗测试和恒流充放电实验,测试材料的电化学性能.结果表明:Li_2Mn_(0.5)Ni_(0.5)O_3材料的首次放电比容量为308.9 mAh·g~(-1),库伦效率为92.1%,循环40圈时容量保持率为93.7%,Li_2Mn_(0.5)Co_(0.5)O_3材料的首次放电比容量为282.6 mAh·g~(-1),库伦效率为98.2%;循环50圈时放电比容量为332.6 mAh·g~(-1),充放电性能较好;Li_2Mn_(0.5)Co_(0.5)O_3材料锂离子扩散电阻小,氧化还原峰极化小,展现出良好的循环稳定性.由此得出结论,Co掺杂所得Li_2Mn_(0.5)Co_(0.5)O_3材料相比于Li_2Mn_(0.5)Ni_(0.5)O_3材料,不仅具有更完好的晶型结构,还有更高的放电比容量、更长的循环寿命以及良好的循环稳定性.
Parts of Mn~(2+) in Li_2MnO_3 were replaced by Co~(2+) and Ni~(2+). Li_2Mn_(0.5)Ni_(0.5)O_3 and Li_2Mn_(0.5)Co_(0.5)O_3 were synthesized by high temperature solid state synthesis. The micromorphology and crystalline structure of the material were observed by SEM and X-ray diffraction. The electrochemical properties of the materials were tested by cyclic voltammetry, AC impedance test and constant current charge-discharge test. Results show that the first discharge specific capacity of Li_2Mn_(0.5)Ni_(0.5)O_3 is 308.9 mAh·g~(-1) with the coulombic efficiency being 92.1%, and the capacity retention rate is 93.7% at the 40 th cycle. The initial discharge specific capacity of Li_2Mn_(0.5)Co_(0.5)O_3 is 282.6 mAh·g~(-1) with the coulombic efficiency being 98.2%, the discharge specific capacity is 332.6 mAh·g~(-1) at 50 th cycle and the charge-discharge performance is better. The lithium ion diffusion resistance of Li_2Mn_(0.5)Co_(0.5)O_3 is small, redox peak polarization is not obvious, and exhibits good cycle stability. Compared with Li_2Mn_(0.5)Ni_(0.5)O_3 material, Li_2Mn_(0.5)Co_(0.5)O_3 not only has a perfect crystal structure, but also has a higher specific discharge capacity, a longer cycle life and good cycle stability.
Parts of Mn~(2+) in Li_2MnO_3 were replaced by Co~(2+) and Ni~(2+). Li_2Mn_(0.5)Ni_(0.5)O_3 and Li_2Mn_(0.5)Co_(0.5)O_3 were synthesized by high temperature solid state synthesis. The micromorphology and crystalline structure of the material were observed by SEM and X-ray diffraction. The electrochemical properties of the materials were tested by cyclic voltammetry, AC impedance test and constant current charge-discharge test. Results show that the first discharge specific capacity of Li_2Mn_(0.5)Ni_(0.5)O_3 is 308.9 mAh·g~(-1) with the coulombic efficiency being 92.1%, and the capacity retention rate is 93.7% at the 40 th cycle. The initial discharge specific capacity of Li_2Mn_(0.5)Co_(0.5)O_3 is 282.6 mAh·g~(-1) with the coulombic efficiency being 98.2%, the discharge specific capacity is 332.6 mAh·g~(-1) at 50 th cycle and the charge-discharge performance is better. The lithium ion diffusion resistance of Li_2Mn_(0.5)Co_(0.5)O_3 is small, redox peak polarization is not obvious, and exhibits good cycle stability. Compared with Li_2Mn_(0.5)Ni_(0.5)O_3 material, Li_2Mn_(0.5)Co_(0.5)O_3 not only has a perfect crystal structure, but also has a higher specific discharge capacity, a longer cycle life and good cycle stability.
引文
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[18]靳素芳,韩恩山,朱令之,等.高温固相法合成锂、铁位掺杂的Li Fe PO4/C[J].电池,2011,(2):66-68.JIN Sufang,HAN Enshan,ZHU Lingzhi,et al.Preparing Li Fe PO4/C doped with lithium and iron sites via high-temperature solid-state method[J].Battery Bimonthly,2011,(2):66-68.(in Chinese)
[19]陶洪亮,米常焕,张迎霞.溶胶-凝胶法合成Li(1-x)NaxMn2O4及其作为水系锂离子电池正极材料的电化学性能[J].无机化学学报,2017,33(7):1147-1152.DOI:10.11862/CJIC.2017.156.TAO Hongliang,MI Changhuan,ZHANG Yingxia.A-queous Li-Ion battery cathode material Li1-xNaxMn2O4prepared by sol-gel method and its electrochemical performance[J].Chinese Journal of Inorganic Chemistry,2017,33(7):1147-1152.DOI:10.11862/CJIC.2017.156.(in Chinese)
[20]袁琦,邹正光,万振东,等.锂离子电池正极材料铁掺杂V6O13的制备及电化学性能[J].材料工程,2018,46(1):106-113.YUAN Qi,ZOU Zhengguang,WAN Zhendong,et al.Synthesis and electrochemical properties of Fe-doped V6O13as cathode material for Lithiumion battery[J].Journal of Materials Engineering,2018,46(1):106-113.(in Chinese)
[21]PADHI A K,NANJUNDASWAMY K S.Phospho-olivines aspositive electrode materials for the rechargeable lithium batteries[J].Journal of the Electrochemical Society,1997,144(4):1188-1194.
[22]白守礼,李欣,文越华,等.电解液对水系可充电池MnO2正极电化学性能的影响[J].物理化学学报,2016,32(8):2007-2017.DOI:10.3866/PKU.WHXB201604261.BAI Shouli,LI Xin,WEN Yuehua,et al.Effect of electrolyte on the electrochemical performance of the MnO2cathode for aqueous rechargeable batteries[J].Acta Physico-Chimica Sinica,2016,32(8):2007-2017.DOI:10.3866/PKU.WHXB201604261.(in Chinese)
[23]TANG W,HOU Y Y,WANG F X,et al.Li Mn2O4nanotube as cathode material of second-level charge capability for aqueous rechargeable batteries[J].Nano Letters,2013,13:2036-2040.DOI:10.1021/nl400199r.
[2]吴楠,张乃庆,刘伶,等.锂离子电池正极材料层状Li MnO2的研究进展[J].功能材料信息,2006(3):19-21.WU Nan,ZHANG Naiqing,LIU Ling,et al.Research progress in layer Li MnO2cathodes for Lithiumion battery[J].Functional Materials Information,2006(3):19-21.(in Chinese)
[3]LI W,DAHN J R,WAINWRIGHT D.Rechargeable lithium batteries with aqueous-electrolytes[J].Science,1994(264):1115-1118.DOI:10.1126/science.264.5162.1115.
[4]WANG G X,ZHONG S,BRADHURST D H,et al.Secondary aqueous lithium-ion batteries with spinel anodes and cathodes[J].Journal of Power Sources,1998(74):198-201.DOI:10.1016/S0378-7753(98)00057-3.
[5]WANG P,YANG H,YANG H Q.Electrochemical behavior of Li-Mn spinel electrode material in aqueous solution[J].Journal of Power Sources,1996(63):275-278.
[6]LI N C,PATRISSI C J,CHE G L,et al.Rate capabilities of nanostructured Li Mn2O4electrodes in aqueous electrolyte[J].Journal of the Electrochemical Society,2000(147):2044-2049.
[7]MINAKSHI M,SINGH P,ISSA T B,et al.Lithium insertion into manganese dioxide electrode in MnO2/Zn aqueous battery:PartⅢ.electrochemical behavior ofγ-MnO2in aqueous lithium hydroxide electrolyte[J].Journal of Power Sources,2006,153(1):165-169.DOI:10.1016/j.jpowsour.2003.12.018.
[8]LI Zhihua,WANG Liqiu,LI Keyan,et al.Li Mn2O4rodsas cathode materials with high rate capability and good cycling performance in aqueous electrolyte[J].Journal of Alloys and Comounds,2013(580):592-597.
[9]赵艳琴,朱靖.水系锂离子电池正极材料的制备及电性能[J].河北联合大学学报(自然科学版),2015,37(2):55-61.ZHAO Yanqin,ZHU Jing.Electrochemstry synthesis and characterization of cathode material for Lithium-ion batteries in water system[J].Journal of Hebei United University(Natural Science Edition),2015,37(2):55-61.(in Chinese)
[10]王焕焕,许倩,张玉,等.纳米锰酸锂的制备及在水系锂离子电池中的电化学性能研究[J].安康学院学报,2017,29(1):107-111.DOI:10.16858/j.issn.1674-0092.2017.01.023.WANG Huanhuan,XU Qian,ZHANG Yu,et al.Synthesis and electrochemical investigation of NanoLi Mn2O4as cathode materials for aqueous Lithium-ion batteries[J].Journal of Ankang University,2017,29(1):107-111.DOI:10.16858/j.issn.1674-0092.2017.01.023.(in Chinese)
[11]林晓静,李淑华,何泽珍,等.锂离子电池正极材料层状氧化锰锂的研究进展[J].化工科技,2003(6):43-48.LIN Xiaojing,LI Shuhua,HE Zezhen,et al.Progress on layered lithium manganese oxide as cathode material of lithium-ion rechargeable batteries[J].Science&Technology in Chemical Industry,2003(6):43-48.(in Chinese)
[12]唐致远,周征,李建刚,等.掺杂元素对锰酸锂电极材料性能的影响[J].电源技术,2002,(z1):203-205.TANG Zhiyuan,ZHOU Zheng,LI Jiangang,et al.Effect of doping elements on properties of Li Mn2O4as cathode material[J].Chinese Journal of Power Sources,2002(z1):203-205.(in Chinese)
[13]耿树东,翟玉春.Co掺杂对锂离子电池材料Li Mn2O4性能的影响[J].材料与冶金学报,2014,13(3):233-236.GENG Shudong,ZHAI Yuchun.Effect of cobalt doping on the performance of lithium ion battery material Li Mn2O4[J].Journal of Materials and Metallurgy,2014,13(3):233-236.(in Chinese)
[14]钟辉,许惠,汪文成,等.掺镍型层状LixNiyMn1-yO2正极材料的合成与电性能研究[J].无机化学学报,2003(4):441-444.ZHONG Hui,XU Hui,WANG Wencheng,et al.Studies on the layered Lix Niy Mn1-yO2cathode material:synthesis,structure and electrochemical properties[J].Chinese Journal of Inorganic Chemistry,2003(4):441-444.(in Chinese)
[15]何智峰,赵彦明,陈玲,等.锂离子电池正极材料Li3V2-xNix(PO4)3的制备及其性能[J].电源技术,2009(5):401-405.HE Zhifeng,ZHAO Yanming,CHEN Ling,et al.Preparation and performance of Li3V2-xNix(PO4)3cathode material for lithium-ion batteries[J].Chinese Journal of Power Sources,2009(5):401-405.(in Chinese)
[16]李为立.溶胶凝胶法制备膜支撑凝胶聚合物电解质及其性能研究[J].江苏科技大学学报(自然科学版),2008,22(1):43-47.LI Weili.Novel membrane supporting hybrid gel electrolyte prepared with in-situ sol-gel method[J].Journal of Jiangsu University of Science and Technology(Natural Science Edition),2008,22(1):43-47.(in Chinese)
[17]盛锁江,王振伟,耿海龙,等.高温固相法合成Li Ni0.6CO0.2Mn0.2O2的电化学性能[J].电池,2017(4):196-198.DOI:10.19535/j.1001-1579.2017.04.002.SHENG Suojiang,WANG Zhenwei,GENG Hailong,et al.Electrochemical performance of Li Ni0.6Co0.2Mn0.2O2synthesized via high-temperature solid-state method[J].Battery Bimonthly,2017,(4):196-198.DOI:10.19535/j.1001-1579.2017.04.002.(in Chinese)
[18]靳素芳,韩恩山,朱令之,等.高温固相法合成锂、铁位掺杂的Li Fe PO4/C[J].电池,2011,(2):66-68.JIN Sufang,HAN Enshan,ZHU Lingzhi,et al.Preparing Li Fe PO4/C doped with lithium and iron sites via high-temperature solid-state method[J].Battery Bimonthly,2011,(2):66-68.(in Chinese)
[19]陶洪亮,米常焕,张迎霞.溶胶-凝胶法合成Li(1-x)NaxMn2O4及其作为水系锂离子电池正极材料的电化学性能[J].无机化学学报,2017,33(7):1147-1152.DOI:10.11862/CJIC.2017.156.TAO Hongliang,MI Changhuan,ZHANG Yingxia.A-queous Li-Ion battery cathode material Li1-xNaxMn2O4prepared by sol-gel method and its electrochemical performance[J].Chinese Journal of Inorganic Chemistry,2017,33(7):1147-1152.DOI:10.11862/CJIC.2017.156.(in Chinese)
[20]袁琦,邹正光,万振东,等.锂离子电池正极材料铁掺杂V6O13的制备及电化学性能[J].材料工程,2018,46(1):106-113.YUAN Qi,ZOU Zhengguang,WAN Zhendong,et al.Synthesis and electrochemical properties of Fe-doped V6O13as cathode material for Lithiumion battery[J].Journal of Materials Engineering,2018,46(1):106-113.(in Chinese)
[21]PADHI A K,NANJUNDASWAMY K S.Phospho-olivines aspositive electrode materials for the rechargeable lithium batteries[J].Journal of the Electrochemical Society,1997,144(4):1188-1194.
[22]白守礼,李欣,文越华,等.电解液对水系可充电池MnO2正极电化学性能的影响[J].物理化学学报,2016,32(8):2007-2017.DOI:10.3866/PKU.WHXB201604261.BAI Shouli,LI Xin,WEN Yuehua,et al.Effect of electrolyte on the electrochemical performance of the MnO2cathode for aqueous rechargeable batteries[J].Acta Physico-Chimica Sinica,2016,32(8):2007-2017.DOI:10.3866/PKU.WHXB201604261.(in Chinese)
[23]TANG W,HOU Y Y,WANG F X,et al.Li Mn2O4nanotube as cathode material of second-level charge capability for aqueous rechargeable batteries[J].Nano Letters,2013,13:2036-2040.DOI:10.1021/nl400199r.
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