稀土La掺杂对层状富锂锰基氧化物正极材料结构及电化学性能的影响
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摘要
采用碳酸盐共沉淀-高温烧结法制备了La掺杂层状富锂锰基氧化物正极材料Li_(1.2)Mn_(0.54-x)Ni_(0.13)Co_(0.13)La_xO_2(x=0,0.01,0.03,0.05),考察了La掺杂量对正极材料的结构及电化学性能的影响.采用X射线衍射(XRD)和扫描电镜(SEM)分析研究了正极材料的结构和形貌特征,材料的电化学性能采用交流阻抗和充放电测试仪进行测试分析.研究结果表明:所有样品均保持层状α-NaFeO_2结构,随着La掺杂量的增加,样品形貌未发生明显变化,样品放电容量呈现先增大后降低的趋势,当La掺杂量为0.03时,具有最高的放电比容量285.3 mAh/g(0.1 C),经过50次循环后的放电比容量为260.5 mAh/g,容量保持率为91.3%.
La doping Li_(1.2)Mn_(0.54-x)Ni_(0.13)Co_(0.13)La_xO_2(x =0, 0.01,0.03,0.05) layered Li-rich Mn-based oxide cathode materials were prepared by carbonate coprecipitation-high temperature sintering method. The effect of La doping on the structure and electrochemical properties of cathode materials was investigated. The structures and morphologies of cathode materials were analyzed by the X-ray diffraction(XRD) and scanning electron microscopy(SEM), electrochemical properties of materials were tested by AC Impedance and Charge and Discharge Tester. The results show that layered α-NaFeO_2 structure is maintained in all samples, and the morp hology of samples does not change obviously with the increase of La doping amount. However, the discharge capacity of samples increases first and then decreases. They obtain the highest discharge specific capacity of 285.3 mAh/g(0.1C) when the doping amount of La is 0.03. The specific discharge capacity is 260.5 mAh/g after 50 cycles and the capacity retention ratio is 91.3 %.
La doping Li_(1.2)Mn_(0.54-x)Ni_(0.13)Co_(0.13)La_xO_2(x =0, 0.01,0.03,0.05) layered Li-rich Mn-based oxide cathode materials were prepared by carbonate coprecipitation-high temperature sintering method. The effect of La doping on the structure and electrochemical properties of cathode materials was investigated. The structures and morphologies of cathode materials were analyzed by the X-ray diffraction(XRD) and scanning electron microscopy(SEM), electrochemical properties of materials were tested by AC Impedance and Charge and Discharge Tester. The results show that layered α-NaFeO_2 structure is maintained in all samples, and the morp hology of samples does not change obviously with the increase of La doping amount. However, the discharge capacity of samples increases first and then decreases. They obtain the highest discharge specific capacity of 285.3 mAh/g(0.1C) when the doping amount of La is 0.03. The specific discharge capacity is 260.5 mAh/g after 50 cycles and the capacity retention ratio is 91.3 %.
引文
[1]OZAWA K.Lithium-ion rechargeable batteries with LiCoO2and car bon electrodes-the LiCoO2-C system[J].Solid State Ionics,1994,69(3):212-221.
[2]KEMP J,COX P.Electronic structure of LiCoO2and related materials;photoemission studies[J].Journal of Physics-Condensed Matter,1990,2(48):9653-9667.
[3]SEKAI K,AZUMA H,OMARU A,et al.Lithium-ion rechargeable cells with LiCoO2and carbon electrodes[J].Journal of Power Sources,1993,43(1/2/3):241-244.
[4]DELMAS C,BRACONNIER J J,HAGENMULLER P.A new variety of LiCoO2with an unusual oxygen packing obtained by exchange reaction[J].Materials Research Bulletin,1982,17(1):117-123.
[5]MOORE R J,WHITE J.Equilibrium relationships in the systems Li-CoO and Li-Ni-O[J].Journal of Materials Science,1974,9(1):1401-1408.
[6]CHEN C,KELDER E M,SCHOONMAN J,et al.Morphology control of thin LiCoO2films fabricated using the electrostatic spray deposition(ESD)technique[J].Journal of Materials Chemistry,1996,6(5):765-771.
[7]WANG J J,SUN X L.Understanding and recent development of carbon coating on LiFePO4cathode materials for lithium-ion batteries[J].Energy Environmental Science,2012,5(1):5163-5185.
[8]WANG D,LI H,SHI S,et al.Improving the rate performance of LiFePO4by Fe-site doping[J].Electrochimica Acta,2005,50(14):2955-2958.
[9]GELLER S,DURAND J.Refinement of the structure of LiMnPO4[J].Acta Crystallographica,1960,13(4):325-331.
[10]BRAMNIK N N,BRAMNIK K G,BUHRMESTER T,et al.Electrochemical and structural study of LiCoPO4-based electrodes[J].Journal of Solid State Electrochemistry,2004,8(8):558-564.
[11]BAKENOV Z,TANIGUCHI I.Electrochemical performance of nanocomposite LiMnPO4/C cathode materials for lithium batteries[J].Electrochemistry Communications,2010,12(1):75-78.
[12]JIN B,GU H B,KIM K W.Effect of different conductive additives on charge/discharge properties of LiCoPO4/Li batteries[J].Journal of Solid State Electrochemistry,2008,12(2):105-111.
[13]OHZUKU T,MAKIMURA Y.Layered Lithium Insertion Material of LiNi1/3Co1/3Mn1/3O2for Lithium-Ion Batteries[J].Chemistry Letters,2001,30(7):642-644.
[14]SHAJU K M,RAO G V,CHOWDARI B.Performance of layered LiNi1/3Co1/3Mn1/3O2as cathode for Li-ion batteries[J].Electrochimica Acta,2002,48(2):145-151.
[15]LI Y J,HAN Q,MING X Q,et al.Synthesis and characterization of LiNi0.5Co0.2Mn0.3O2cathode material prepared by a novel hydrothermal process[J].Ceramics International,2014(40):14933-14938.
[16]NOH M,CHO J.Optimized synthetic conditions of LiNi0.5Co0.2Mn0.3O2cathode materials for high rate lithium batteries via Co-precipitation method[J].Journal of The Electrochemical Society,2012,160(1):105-111.
[17]YANG C F,HUANG J J,HUANG L G,et al.Electrochemical performance of LiCo1/3Co1/3Mn1/3O2hollow spheres as cathode material forlithium ion batteries[J].Journal of Power Sources,2013,226:219-222.
[18]LEE K S,MYUNG S T,PRAKASH J,et al.Optimization of microwave synthesis of Li[Ni0.4Co0.2Mn0.4]O2as a positive electrode material for lithium batteries[J].Electrochimica Acta,2008,53(7):3065-3074.
[19]FU C Y,ZHOU Z L,LIU Y H,et al.Synthesis and electrochemical properties of Mg-doped LiNi0.6Co0.2Mn0.2O2cathode materials for Li-ion battery[J].Journal of Wuhan University of Technology,2011,26(2):211-215.
[20]MYUNG S T,IZUMI K,KOMABA S,et al.Role of alumina coating on Li-Ni-Co-Mn-O particles as positive electrode material for lithium-ion batteries[J].Chemistry of Materials,2005,17(14):3695-3704.
[21]ZHENG J M,LI J,ZHANG Z R,et al.The effects of TiO2coating on the electrochemical performance of Li[Li0.2Mn0.54Ni0.13Co0.13]O2cathode material for lithium-ion battery[J].Solid State Ionics,2008,179(27-32):1794-1799.
[22]WU Y,MURUGAN A V,MANTHIRAM A.Surface modification of high capacity layered Li[Li0.2Mn0.54Ni0.13Co0.13]O2cathodes by AlPO4[J].Journal of The Electrochemical Society,2008,155(9):A635-A641.
[23]LIU J,WANG Q Y.Carbon-coated high capacity layeredLi[Li0.2Mn0.54Ni0.13Co0.13]O2cathodes[J].Electrochemistry Communications,2010,12(6):750-753.
[24]LIU J,REEJA J B,MANTHIRAM A.Conductive surface modification with aluminum of high capacity layered Li[Li0.2Mn0.54Ni0.13Co0.13]O2cathodes[J].Journal of Physical Chemistry C,2010,114(20):9528-9533.
[25]JIAO L F,ZHANG M,YUAN H T,et al.Effect of Cr doping on the structural,electrochemical properties of Li[Li0.2Ni0.2-x/2Mn0.6-x/2Crx]O2(x=0,0.02,0.04,0.06,0.08)as cathode materials for lithium secondary batteries[J].Journal of Power Sources,2007,167(1):178-184.
[26]PARK S H,SUN Y K.Synthesis and electrochemical properties of layered Li[Li0.25Ni(0.275-x/2)AlxMn(0.575-x/2)]O2materials prepared by SolGel method[J].Journal of Power Sources,2003,119(21):161-165.
[27]KANG S H,THACKERAY M M.Stabilization of x Li2MnO3·(1-x)LiMO2electrode surfaces(M=Mn,Ni,Co)with mildly acidic,fluorinated solutions[J].Journal of The Electrochemical Society,2008,155(4):A269-A275.
[28]KANG S H,AMINE K.Layered Li(Li0.2Ni0.15+0.5zCo0.10Mn0.55-0.5z)O2-z Fz cathode materials for Li-ion secondary batteries[J].Journal of Power Sources,2005,146(1/2):654-657.
[29]钟盛文,黎明旭,张骞,等.富锂锰基正极材料的高温储存性能研究[J].有色金属科学与工程,2013,4(3):45-48.
[30]徐宝和,吴甜甜,钟盛文,等.Si4+掺杂对富锂Li[Li0.15Mn0.575Ni0.275]1-x SixO2材料性能的影响[J].有色金属科学与工程,2012,3(2):25-27.
[31]GHULAM F,GHULAM M,MUHAMMAD U,et al.Effect of Ladoping on the structural,morphological and electrochemical properties of LiCoO2nanoparticles using Sol-Gel technique[J].Materials Research Express,2018,5:055044.
[32]张海朗,安静.稀土La元素掺杂对锂离子电池正极材料LiMn2O4性能的影响[J].功能材料,2009,40(2):507-508.
[33]廖春发,陈辉煌,陈子发,等.稀土掺杂锂离子正极材料LiCoO2的影响研究[J].江西有色金属,2004,18(2):33-37.
[34]桂阳海,胡国荣,赵恒勤,等.稀土掺杂锂离子电池正极材料锂镍钴氧的研究[J].矿产保护与利用,2003,4(2):41-44.
[35]刘晓红,项玲芳,高军,等.稀土元素La掺杂材料LiCoPO4的性能研究[J].矿冶工程,2011,31(3):108-110.
[36]DENG H,BELHAROUAK I,SUN Y K,et al.LixNi0.25Mn0.75Oy(0.5≤x≤2,2≤y≤2.75)compounds for high-energy lithium-ion batteries[J].Journal of Materials Chemistry,2009,19(26):4510-4516.
[37]JARVIS K A,DENG Z,ALLARD L F,et al.Atomic structure of a lithium-rich layered oxide material for lithium-ion batteries:evidence of a solid solution[J].Journal of Materials Chemistry,2011,23(16):3614-3621.
[38]LU Z,MACNEIL D D,DAHN J R.Layered cathode materials Li[NixLi(1/3-2x/3)Mn(2/3-x/3)]O2for llithium-ion batteries[J].Electrochemical and Solid State Letters,2001,4(11):A191-A194.
[39]MYUNG S T,IZUMI K,KOMABA S,et al.Role of alumina coating on LiNi-Co-Mn-O particles as positive electrode material for lithium-ion batteries[J].Journal of Materials Chemistry,2005,17(14):3695-3704.
[40]DING Y,ZHANG P,JIANG Y,et al.Effect of rare earth elements doping on structure and electrochemical properties of LiNi1/3Co1/3Mn1/3O for lithium-ion battery[J].Solid State Ionic,2007,178:967-971.
[41]LI N,AN R,SU Y F,et al.The role of yttrium content in improving electrochemical performance of layered lithium-rich cathode materials for Li-ion batteries[J].Journal of Materials Chemistry A,2013,1:9760-9767.
[42]SPEIGHT J G.Lange′s handbook of chemistry[M].New York:Mc Graw-Hill:2005.
[43]DENG Z Q,MANTHIRAM A.Influence of cationic substitutions on the oxygen loss and reversible capacity of Lithium-rich layered oxide cathodes[J].Journal of Physical Chemistry C,2011,115(14):7097-7103.
[44]WU F,LI N,SU Y,et al.Can surface modification be more effective to enhance the electrochemical performance of lithium rich materials[J].Journal of Materials Chemistry,2012,22(4):1489-1497.
[2]KEMP J,COX P.Electronic structure of LiCoO2and related materials;photoemission studies[J].Journal of Physics-Condensed Matter,1990,2(48):9653-9667.
[3]SEKAI K,AZUMA H,OMARU A,et al.Lithium-ion rechargeable cells with LiCoO2and carbon electrodes[J].Journal of Power Sources,1993,43(1/2/3):241-244.
[4]DELMAS C,BRACONNIER J J,HAGENMULLER P.A new variety of LiCoO2with an unusual oxygen packing obtained by exchange reaction[J].Materials Research Bulletin,1982,17(1):117-123.
[5]MOORE R J,WHITE J.Equilibrium relationships in the systems Li-CoO and Li-Ni-O[J].Journal of Materials Science,1974,9(1):1401-1408.
[6]CHEN C,KELDER E M,SCHOONMAN J,et al.Morphology control of thin LiCoO2films fabricated using the electrostatic spray deposition(ESD)technique[J].Journal of Materials Chemistry,1996,6(5):765-771.
[7]WANG J J,SUN X L.Understanding and recent development of carbon coating on LiFePO4cathode materials for lithium-ion batteries[J].Energy Environmental Science,2012,5(1):5163-5185.
[8]WANG D,LI H,SHI S,et al.Improving the rate performance of LiFePO4by Fe-site doping[J].Electrochimica Acta,2005,50(14):2955-2958.
[9]GELLER S,DURAND J.Refinement of the structure of LiMnPO4[J].Acta Crystallographica,1960,13(4):325-331.
[10]BRAMNIK N N,BRAMNIK K G,BUHRMESTER T,et al.Electrochemical and structural study of LiCoPO4-based electrodes[J].Journal of Solid State Electrochemistry,2004,8(8):558-564.
[11]BAKENOV Z,TANIGUCHI I.Electrochemical performance of nanocomposite LiMnPO4/C cathode materials for lithium batteries[J].Electrochemistry Communications,2010,12(1):75-78.
[12]JIN B,GU H B,KIM K W.Effect of different conductive additives on charge/discharge properties of LiCoPO4/Li batteries[J].Journal of Solid State Electrochemistry,2008,12(2):105-111.
[13]OHZUKU T,MAKIMURA Y.Layered Lithium Insertion Material of LiNi1/3Co1/3Mn1/3O2for Lithium-Ion Batteries[J].Chemistry Letters,2001,30(7):642-644.
[14]SHAJU K M,RAO G V,CHOWDARI B.Performance of layered LiNi1/3Co1/3Mn1/3O2as cathode for Li-ion batteries[J].Electrochimica Acta,2002,48(2):145-151.
[15]LI Y J,HAN Q,MING X Q,et al.Synthesis and characterization of LiNi0.5Co0.2Mn0.3O2cathode material prepared by a novel hydrothermal process[J].Ceramics International,2014(40):14933-14938.
[16]NOH M,CHO J.Optimized synthetic conditions of LiNi0.5Co0.2Mn0.3O2cathode materials for high rate lithium batteries via Co-precipitation method[J].Journal of The Electrochemical Society,2012,160(1):105-111.
[17]YANG C F,HUANG J J,HUANG L G,et al.Electrochemical performance of LiCo1/3Co1/3Mn1/3O2hollow spheres as cathode material forlithium ion batteries[J].Journal of Power Sources,2013,226:219-222.
[18]LEE K S,MYUNG S T,PRAKASH J,et al.Optimization of microwave synthesis of Li[Ni0.4Co0.2Mn0.4]O2as a positive electrode material for lithium batteries[J].Electrochimica Acta,2008,53(7):3065-3074.
[19]FU C Y,ZHOU Z L,LIU Y H,et al.Synthesis and electrochemical properties of Mg-doped LiNi0.6Co0.2Mn0.2O2cathode materials for Li-ion battery[J].Journal of Wuhan University of Technology,2011,26(2):211-215.
[20]MYUNG S T,IZUMI K,KOMABA S,et al.Role of alumina coating on Li-Ni-Co-Mn-O particles as positive electrode material for lithium-ion batteries[J].Chemistry of Materials,2005,17(14):3695-3704.
[21]ZHENG J M,LI J,ZHANG Z R,et al.The effects of TiO2coating on the electrochemical performance of Li[Li0.2Mn0.54Ni0.13Co0.13]O2cathode material for lithium-ion battery[J].Solid State Ionics,2008,179(27-32):1794-1799.
[22]WU Y,MURUGAN A V,MANTHIRAM A.Surface modification of high capacity layered Li[Li0.2Mn0.54Ni0.13Co0.13]O2cathodes by AlPO4[J].Journal of The Electrochemical Society,2008,155(9):A635-A641.
[23]LIU J,WANG Q Y.Carbon-coated high capacity layeredLi[Li0.2Mn0.54Ni0.13Co0.13]O2cathodes[J].Electrochemistry Communications,2010,12(6):750-753.
[24]LIU J,REEJA J B,MANTHIRAM A.Conductive surface modification with aluminum of high capacity layered Li[Li0.2Mn0.54Ni0.13Co0.13]O2cathodes[J].Journal of Physical Chemistry C,2010,114(20):9528-9533.
[25]JIAO L F,ZHANG M,YUAN H T,et al.Effect of Cr doping on the structural,electrochemical properties of Li[Li0.2Ni0.2-x/2Mn0.6-x/2Crx]O2(x=0,0.02,0.04,0.06,0.08)as cathode materials for lithium secondary batteries[J].Journal of Power Sources,2007,167(1):178-184.
[26]PARK S H,SUN Y K.Synthesis and electrochemical properties of layered Li[Li0.25Ni(0.275-x/2)AlxMn(0.575-x/2)]O2materials prepared by SolGel method[J].Journal of Power Sources,2003,119(21):161-165.
[27]KANG S H,THACKERAY M M.Stabilization of x Li2MnO3·(1-x)LiMO2electrode surfaces(M=Mn,Ni,Co)with mildly acidic,fluorinated solutions[J].Journal of The Electrochemical Society,2008,155(4):A269-A275.
[28]KANG S H,AMINE K.Layered Li(Li0.2Ni0.15+0.5zCo0.10Mn0.55-0.5z)O2-z Fz cathode materials for Li-ion secondary batteries[J].Journal of Power Sources,2005,146(1/2):654-657.
[29]钟盛文,黎明旭,张骞,等.富锂锰基正极材料的高温储存性能研究[J].有色金属科学与工程,2013,4(3):45-48.
[30]徐宝和,吴甜甜,钟盛文,等.Si4+掺杂对富锂Li[Li0.15Mn0.575Ni0.275]1-x SixO2材料性能的影响[J].有色金属科学与工程,2012,3(2):25-27.
[31]GHULAM F,GHULAM M,MUHAMMAD U,et al.Effect of Ladoping on the structural,morphological and electrochemical properties of LiCoO2nanoparticles using Sol-Gel technique[J].Materials Research Express,2018,5:055044.
[32]张海朗,安静.稀土La元素掺杂对锂离子电池正极材料LiMn2O4性能的影响[J].功能材料,2009,40(2):507-508.
[33]廖春发,陈辉煌,陈子发,等.稀土掺杂锂离子正极材料LiCoO2的影响研究[J].江西有色金属,2004,18(2):33-37.
[34]桂阳海,胡国荣,赵恒勤,等.稀土掺杂锂离子电池正极材料锂镍钴氧的研究[J].矿产保护与利用,2003,4(2):41-44.
[35]刘晓红,项玲芳,高军,等.稀土元素La掺杂材料LiCoPO4的性能研究[J].矿冶工程,2011,31(3):108-110.
[36]DENG H,BELHAROUAK I,SUN Y K,et al.LixNi0.25Mn0.75Oy(0.5≤x≤2,2≤y≤2.75)compounds for high-energy lithium-ion batteries[J].Journal of Materials Chemistry,2009,19(26):4510-4516.
[37]JARVIS K A,DENG Z,ALLARD L F,et al.Atomic structure of a lithium-rich layered oxide material for lithium-ion batteries:evidence of a solid solution[J].Journal of Materials Chemistry,2011,23(16):3614-3621.
[38]LU Z,MACNEIL D D,DAHN J R.Layered cathode materials Li[NixLi(1/3-2x/3)Mn(2/3-x/3)]O2for llithium-ion batteries[J].Electrochemical and Solid State Letters,2001,4(11):A191-A194.
[39]MYUNG S T,IZUMI K,KOMABA S,et al.Role of alumina coating on LiNi-Co-Mn-O particles as positive electrode material for lithium-ion batteries[J].Journal of Materials Chemistry,2005,17(14):3695-3704.
[40]DING Y,ZHANG P,JIANG Y,et al.Effect of rare earth elements doping on structure and electrochemical properties of LiNi1/3Co1/3Mn1/3O for lithium-ion battery[J].Solid State Ionic,2007,178:967-971.
[41]LI N,AN R,SU Y F,et al.The role of yttrium content in improving electrochemical performance of layered lithium-rich cathode materials for Li-ion batteries[J].Journal of Materials Chemistry A,2013,1:9760-9767.
[42]SPEIGHT J G.Lange′s handbook of chemistry[M].New York:Mc Graw-Hill:2005.
[43]DENG Z Q,MANTHIRAM A.Influence of cationic substitutions on the oxygen loss and reversible capacity of Lithium-rich layered oxide cathodes[J].Journal of Physical Chemistry C,2011,115(14):7097-7103.
[44]WU F,LI N,SU Y,et al.Can surface modification be more effective to enhance the electrochemical performance of lithium rich materials[J].Journal of Materials Chemistry,2012,22(4):1489-1497.
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