高能量密度锂离子电池层状锰基正极材料研究进展
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摘要
层状锰基材料Li[Li_x(MnM)_(1-x)]O_2(M=Ni,Co,Cr,…)以高比容量成为最具应用前景的正极体系之一,近年来成为研究热点而倍受关注,尤其借助原位测试分析等先进表征手段,对Li[Li_x(MnM)_(1-x)]O_2的结构及其高容量获取机理的研究取得显著进展.本文概括介绍了高能量密度层状正极材料的结构与充放电机理,重点针对其目前依然存在的问题,详细归纳了Li[Li_x(MnM)_(1-x)]O_2正极材料充放电循环过程中电压衰减机理、界面/表面特征以及性能改善的研究新进展,而且对高能量密度层状正极材料的未来研究方向也进行了探讨.
Layered Mn-based series Li[Li_x(MnM)_(1- x)]O_2( M = Ni,Co,Cr,…) due to its much higher capacity is one of the very promising candidates of cathodes,which has become a research hotspot recently and attracted more and more attention. Especially,with the aid of advanced characterization techniques including in-situ analysis,studies on the complex structure and high-capacity delivering mechanism of the series have achieved significant progress. In the paper,the structural characterization and charge-discharge behavior of the high-energy density layered cathode were briefly introduced. Study progresses on the voltage degradation,interface / surface variation during cycling and performance improvements of Li[Li_x(MnM)_(1- x)]O_2 were reviewed in detail particularly in view of its exiting issues.Furthermore,the challenges and prospects in the high-energy density layered cathode materials were also discussed herein.
Layered Mn-based series Li[Li_x(MnM)_(1- x)]O_2( M = Ni,Co,Cr,…) due to its much higher capacity is one of the very promising candidates of cathodes,which has become a research hotspot recently and attracted more and more attention. Especially,with the aid of advanced characterization techniques including in-situ analysis,studies on the complex structure and high-capacity delivering mechanism of the series have achieved significant progress. In the paper,the structural characterization and charge-discharge behavior of the high-energy density layered cathode were briefly introduced. Study progresses on the voltage degradation,interface / surface variation during cycling and performance improvements of Li[Li_x(MnM)_(1- x)]O_2 were reviewed in detail particularly in view of its exiting issues.Furthermore,the challenges and prospects in the high-energy density layered cathode materials were also discussed herein.
引文
[1]Lu Z H,Mac Neil D D,Dahn J R.Layered cathode materials Li[NixLi(1/3-2x/3)Mn(2/3-x/3)]O2for lithium-ion batteries.Electrochem Solid State Lett,2001,4(11):A191
[2]Shen C H,Huang L,Lin Z,et al.Kinetics and structural changes of Li-rich layered oxide 0.5 Li2Mn O3·0.5Li Ni0.292Co0.375-Mn0.333O2material investigated by a novel technique combining in situ XRD and a multipotential step.ACS Appl Mater Interfaces,2014,6(15):13271
[3]Lin C K,Piao Y,Kan Y C,et al.Probing thermally induced decomposition of delithiated Li1.2-xNi0.15Mn0.55Co0.1O2by insitu high energy X-ray diffraction.ACS Appl Mater Interfaces,2014,6(15):12692
[4]Yu X Q,Lyu Y C,Gu L,et al.Understanding the rate capability of high-energy-density Li-rich layered Li1.2Ni0.15Co0.1Mn0.55-O2cathode materials.Adv Energy Mater,2014,4(5):1
[5]Shen C H,Wang Q,Fu F,et al.Facile synthesis of the Li-rich layered oxide Li1.23Ni0.09Co0.12Mn0.56O2with superior lithium storage performance and new insights into structural transformation of the layered oxide material during charge-discharge cycle:in situ XRD characterization.ACS Appl Mater Interfaces,2014,6(8):5516
[6]Hy S,Felix F,Rick J,et al.Direct in situ observation of Li2O evolution on Li-rich high-capacity cathode material,Li[NixLi(1-2x)/3Mn(2-x)/3]O2(0≤x≤0.5).J Am Chem Soc,2014,136(3):999
[7]Yang F F,Liu Y J,Martha S K,et al.Nanoscale morphological and chemical changes of high voltage lithium-manganese rich NMC composite cathodes with cycling.Nano Lett,2014,14(8):4334
[8]Yu H J,Zhou H S.High-energy cathode materials(Li2Mn O3-Li MO2)for lithium-ion batteries.J Phys Chem Lett,2013,4(8):1268
[9]Jarvis K A,Deng Z Q,Allard L F,et al.Atomic structure of a lithium-rich layered oxide material for lithium-ion batteries:evidence of a solid solution.Chem Mater,2011,23(16):3614
[10]Gao M,Lian F,Qiu W H,et al.Rate capability of Li[Li0.17Mn0.58Ni0.25]O2as high-capacity cathode materials.J Univ Sci Technol Beijing,2013,35(1):78(高敏,连芳,仇卫华,等.高容量正极材料Li[Li0.17Mn0.58Ni0.25]O2的倍率性能.北京科技大学学报,2013,35(1):78)
[11]Zheng J M,Gu M,Genc A,et al.Mitigating voltage fade in cathode materials by improving the atomic level uniformity of elemental distribution.Nano Lett,2014,14(5):2628
[12]Koga H,Croguennec L,Mannessiez P,et al.Li1.20Mn0.54-Co0.13Ni0.13O2with different particle sizes as attractive positive electrode materials for lithium-ion batteries:insights into their structure.J Phys Chem C,2012,116(25):13497
[13]Long B R,Croy J R,Dogan F,et al.Effect of cooling rates on phase separation in 0.5 Li2Mn O3·0.5Li Co O2electrode materials for Li-ion batteries.Chem Mater,2014,26(11):3565
[14]Yu H J,Ishikawa R,So Y G,et al.Direct atomic-resolution observation of two phases in the Li1.2Mn0.567Ni0.166Co0.067O2cathode material for lithium-ion batteries.Angew Chem Int Ed,2013,52(23):5969
[15]Yoon W S,Kim N,Yang X Q,et al.6Li MAS NMR and in situ X-ray studies of lithium nickel manganese oxides.J Power Sources,2003,119-121:649
[16]Bareo J,Lei C H,Wen J G,et al.Local structure of layered oxide electrode materials for lithium-ion batteries.Adv Mater,2010,22(10):1122
[17]Ohzuku T,Nagayama M,Tsuji K,et al.High-capacity lithium insertion materials of lithium nickel manganese oxides for advanced lithium-ion batteries:toward rechargeable capacity more than 300 m A h g-1.J Mater Chem,2011,21:10179
[18]Johnson C S,Kim J S,Lefief C,et al.The significance of the Li2Mn O3component in‘composite’x Li2Mn O3·(1-x)Li Mn0.5Ni0.5O2electrodes.Electrochem Commun,2004,6(10):1085
[19]Lu Z H,Dahn J R.Understanding the anomalous capacity of Li/Li[NixLi(1/3-2x/3)Mn(2/3-x/3)]O2cells using in situ X-ray diffraction and electrochemical studies.J Electrochem Soc,2002,149(7):A815
[20]Cao T T,Shi C S,Zhao N Q,et al.Understanding the electrochemical properties of Li-rich cathode materials from first-principles calculations.J Phys Chem C,2015,119(52):28749
[21]Armstrong A R,Holzapfel M,Novak P,et al.Demonstrating oxygen loss and associated structural reorganization in the lithium battery cathode Li[Ni0.2Li0.2Mn0.6]O2.J Am Chem Soc,2006,128(26):8694
[22]Yabuuchi N,Yoshii K,Myung S T,et al.Detailed studies of a high-capacity electrode material for rechargeable batteries,Li2Mn O3-Li Co1/3Ni1/3Mn1/3O2.J Am Chem Soc,2011,133(12):4404
[23]Song B H,Day S J,Sui T,et al.Mitigated phase transition during first cycle of a Li-rich layered cathode studied by in operando synchrotron X-ray powder diffraction.Phys Chem Chem Phys,2016,18(6):4745
[24]Mohanty D,Li J L,Abraham D P,et al.Unraveling the voltage-fade mechanism in high-energy-density lithium-ion batteries:origin of the tetrahedral cations for spinel conversion.Chem Mater,2014,26(21):6272
[25]Croy J R,Gallagher K G,Balasubramanian M,et al.Quantifying hysteresis and voltage fade in x Li2Mn O3·(1-x)Li Mn0.5Ni0.5O2electrodes as a function of Li2Mn O3content.J Electrochem Soc,2013,161(3):A318
[26]Bettge M,Li Y,Gallagher K,et al.Voltage fade of layered oxides:its measurement and impact on energy density.J Electrochem Soc,2013,160(11):A2046
[27]Gallagher K G,Croy J R,Balasubramanian M,et al.Correlating hysteresis and voltage fade in lithium-and manganese-rich layered transition-metal oxide electrodes.Electrochem Commun,2013,33:96
[28]Zheng J M,Xu P H,Gu M,et al.Structural and chemical evolution of Li-and Mn-rich layered cathode material.Chem Mater,2015,27(4):1381
[29]Yan P F,Nie A M,Zheng J M,et al.Evolution of lattice structure and chemical composition of the surface reconstruction layer in Li1.2Ni0.2Mn0.6O2cathode material for lithium ion batteries.Nano Lett,2015,15(1):514
[30]Hong J,Lim H D,Lee M,et al.Critical role of oxygen evolved from layered Li-excess metal oxides in lithium rechargeable batteries.Chem Mater,2012,24(14):2692
[31]Castel E,Berg E J,El Kazzi M E,et al.Differential electrochemical mass spectrometry study of the interface of x Li2Mn O3·(1-x)Li MO2(M=Ni,Co,and Mn)material as a positive electrode in Li-ion batteries.Chem Mater,2014,26(17):5051
[32]Lee D J,Im D M,Ryu Y G,et al.Phosphorus derivatives as electrolyte additives for lithium-ion battery:The removal of O2generated from lithium-rich layered oxide cathode.J Power Sources,2013,243:831
[33]Wang Q Y,Liu J,Murugan A V,et al.High capacity doublelayer surface modified Li[Li0.2Mn0.54Ni0.13Co0.13]O2cathode with improved rate capability.J Mater Chem,2009,19(28):4965
[34]Lian F,Gao M,Ma L L,et al.The effect of surface modification on high capacity Li1.375Ni0.25Mn0.75O2+γcathode material for lithium-ion batteries.J Alloys Compd,2014,608:158
[35]Wu Y,Manthiram A.Effect of surface modifications on the layered solid solution cathodes(1-z)Li[Li1/3Mn2/3]O2-z Li[Mn0.5-yNi0.5-yCo2y]O2.Solid State Ionics,2009,180(1):50
[36]Jin Y C,Duh J G.Fluorination induced the surface segregation of high voltage spinel on lithium-rich layered cathodes for enhanced rate capability in lithium ion batteries.ACS Appl Mater Interfaces,2016,8(6):3883
[37]Kobayashi G,Irii Y,Matsumoto F,et al.Improving cycling performance of Li-rich layered cathode materials through combination of Al2O3-based surface modification and stepwise precycling.J Power Sources,2016,303:250
[38]Kim D H,Sandi G,Croy J R,et al.Composite‘layered-layered-spinel’cathode structures for lithium-ion batteries.J Electrochem Soc,2013,160(1):A31
[39]Luo D,Li G S,Fu C C,et al.A new spinel-layered Li-rich microsphere as a high-rate cathode material for Li-ion batteries.Adv Energy Mater,2014,4(11):1400062
[40]Bian X F,Fu Q,Qiu H L,et al.High-performance Li(Li0.18Ni0.15Co0.15Mn0.52)O2@Li4M5O12heterostructured cathode material coated with a lithium borate oxide glass layer.Chem Mater,2015,27(16):5745
[41]Zhao E Y,Liu X F,Hu Z B,et al.Facile synthesis and enhanced electrochemical performances of Li2Ti O3-coated lithiumrich layered Li1.13Ni0.30Mn0.57O2cathode materials for lithiumion batteries.J Power Sources,2015,294:141
[42]Jung Y S,Cavanagh A S,Yan Y F,et al.Effects of atomic layer deposition of Al2O3on the Li[Li0.20Mn0.54Ni0.13Co0.13]O2cathode for lithium-ion batteries.J Electrochem Soc,2011,158(12):A1298
[43]Liu H,Du C Y,Yin G P,et al.An Li-rich oxide cathode material with mosaic spinel grain and a surface coating for high performance Li-ion batteries.J Mater Chem A,2014,2(37):15640
[44]Wu F,Li N,Su Y F,et al.Ultrathin spinel membrane-encapsulated layered lithium-rich cathode material for advanced Li-ion batteries.Nano Lett,2014,14(6):3550
[45]Wu Y,Murugan A V,Manthiram A.Surface modification of high capacity layered Li[Li0.2Mn0.54Ni0.13Co0.13]O2cathodes by Al PO4.J Electrochem Soc,2008,155(9):A635
[2]Shen C H,Huang L,Lin Z,et al.Kinetics and structural changes of Li-rich layered oxide 0.5 Li2Mn O3·0.5Li Ni0.292Co0.375-Mn0.333O2material investigated by a novel technique combining in situ XRD and a multipotential step.ACS Appl Mater Interfaces,2014,6(15):13271
[3]Lin C K,Piao Y,Kan Y C,et al.Probing thermally induced decomposition of delithiated Li1.2-xNi0.15Mn0.55Co0.1O2by insitu high energy X-ray diffraction.ACS Appl Mater Interfaces,2014,6(15):12692
[4]Yu X Q,Lyu Y C,Gu L,et al.Understanding the rate capability of high-energy-density Li-rich layered Li1.2Ni0.15Co0.1Mn0.55-O2cathode materials.Adv Energy Mater,2014,4(5):1
[5]Shen C H,Wang Q,Fu F,et al.Facile synthesis of the Li-rich layered oxide Li1.23Ni0.09Co0.12Mn0.56O2with superior lithium storage performance and new insights into structural transformation of the layered oxide material during charge-discharge cycle:in situ XRD characterization.ACS Appl Mater Interfaces,2014,6(8):5516
[6]Hy S,Felix F,Rick J,et al.Direct in situ observation of Li2O evolution on Li-rich high-capacity cathode material,Li[NixLi(1-2x)/3Mn(2-x)/3]O2(0≤x≤0.5).J Am Chem Soc,2014,136(3):999
[7]Yang F F,Liu Y J,Martha S K,et al.Nanoscale morphological and chemical changes of high voltage lithium-manganese rich NMC composite cathodes with cycling.Nano Lett,2014,14(8):4334
[8]Yu H J,Zhou H S.High-energy cathode materials(Li2Mn O3-Li MO2)for lithium-ion batteries.J Phys Chem Lett,2013,4(8):1268
[9]Jarvis K A,Deng Z Q,Allard L F,et al.Atomic structure of a lithium-rich layered oxide material for lithium-ion batteries:evidence of a solid solution.Chem Mater,2011,23(16):3614
[10]Gao M,Lian F,Qiu W H,et al.Rate capability of Li[Li0.17Mn0.58Ni0.25]O2as high-capacity cathode materials.J Univ Sci Technol Beijing,2013,35(1):78(高敏,连芳,仇卫华,等.高容量正极材料Li[Li0.17Mn0.58Ni0.25]O2的倍率性能.北京科技大学学报,2013,35(1):78)
[11]Zheng J M,Gu M,Genc A,et al.Mitigating voltage fade in cathode materials by improving the atomic level uniformity of elemental distribution.Nano Lett,2014,14(5):2628
[12]Koga H,Croguennec L,Mannessiez P,et al.Li1.20Mn0.54-Co0.13Ni0.13O2with different particle sizes as attractive positive electrode materials for lithium-ion batteries:insights into their structure.J Phys Chem C,2012,116(25):13497
[13]Long B R,Croy J R,Dogan F,et al.Effect of cooling rates on phase separation in 0.5 Li2Mn O3·0.5Li Co O2electrode materials for Li-ion batteries.Chem Mater,2014,26(11):3565
[14]Yu H J,Ishikawa R,So Y G,et al.Direct atomic-resolution observation of two phases in the Li1.2Mn0.567Ni0.166Co0.067O2cathode material for lithium-ion batteries.Angew Chem Int Ed,2013,52(23):5969
[15]Yoon W S,Kim N,Yang X Q,et al.6Li MAS NMR and in situ X-ray studies of lithium nickel manganese oxides.J Power Sources,2003,119-121:649
[16]Bareo J,Lei C H,Wen J G,et al.Local structure of layered oxide electrode materials for lithium-ion batteries.Adv Mater,2010,22(10):1122
[17]Ohzuku T,Nagayama M,Tsuji K,et al.High-capacity lithium insertion materials of lithium nickel manganese oxides for advanced lithium-ion batteries:toward rechargeable capacity more than 300 m A h g-1.J Mater Chem,2011,21:10179
[18]Johnson C S,Kim J S,Lefief C,et al.The significance of the Li2Mn O3component in‘composite’x Li2Mn O3·(1-x)Li Mn0.5Ni0.5O2electrodes.Electrochem Commun,2004,6(10):1085
[19]Lu Z H,Dahn J R.Understanding the anomalous capacity of Li/Li[NixLi(1/3-2x/3)Mn(2/3-x/3)]O2cells using in situ X-ray diffraction and electrochemical studies.J Electrochem Soc,2002,149(7):A815
[20]Cao T T,Shi C S,Zhao N Q,et al.Understanding the electrochemical properties of Li-rich cathode materials from first-principles calculations.J Phys Chem C,2015,119(52):28749
[21]Armstrong A R,Holzapfel M,Novak P,et al.Demonstrating oxygen loss and associated structural reorganization in the lithium battery cathode Li[Ni0.2Li0.2Mn0.6]O2.J Am Chem Soc,2006,128(26):8694
[22]Yabuuchi N,Yoshii K,Myung S T,et al.Detailed studies of a high-capacity electrode material for rechargeable batteries,Li2Mn O3-Li Co1/3Ni1/3Mn1/3O2.J Am Chem Soc,2011,133(12):4404
[23]Song B H,Day S J,Sui T,et al.Mitigated phase transition during first cycle of a Li-rich layered cathode studied by in operando synchrotron X-ray powder diffraction.Phys Chem Chem Phys,2016,18(6):4745
[24]Mohanty D,Li J L,Abraham D P,et al.Unraveling the voltage-fade mechanism in high-energy-density lithium-ion batteries:origin of the tetrahedral cations for spinel conversion.Chem Mater,2014,26(21):6272
[25]Croy J R,Gallagher K G,Balasubramanian M,et al.Quantifying hysteresis and voltage fade in x Li2Mn O3·(1-x)Li Mn0.5Ni0.5O2electrodes as a function of Li2Mn O3content.J Electrochem Soc,2013,161(3):A318
[26]Bettge M,Li Y,Gallagher K,et al.Voltage fade of layered oxides:its measurement and impact on energy density.J Electrochem Soc,2013,160(11):A2046
[27]Gallagher K G,Croy J R,Balasubramanian M,et al.Correlating hysteresis and voltage fade in lithium-and manganese-rich layered transition-metal oxide electrodes.Electrochem Commun,2013,33:96
[28]Zheng J M,Xu P H,Gu M,et al.Structural and chemical evolution of Li-and Mn-rich layered cathode material.Chem Mater,2015,27(4):1381
[29]Yan P F,Nie A M,Zheng J M,et al.Evolution of lattice structure and chemical composition of the surface reconstruction layer in Li1.2Ni0.2Mn0.6O2cathode material for lithium ion batteries.Nano Lett,2015,15(1):514
[30]Hong J,Lim H D,Lee M,et al.Critical role of oxygen evolved from layered Li-excess metal oxides in lithium rechargeable batteries.Chem Mater,2012,24(14):2692
[31]Castel E,Berg E J,El Kazzi M E,et al.Differential electrochemical mass spectrometry study of the interface of x Li2Mn O3·(1-x)Li MO2(M=Ni,Co,and Mn)material as a positive electrode in Li-ion batteries.Chem Mater,2014,26(17):5051
[32]Lee D J,Im D M,Ryu Y G,et al.Phosphorus derivatives as electrolyte additives for lithium-ion battery:The removal of O2generated from lithium-rich layered oxide cathode.J Power Sources,2013,243:831
[33]Wang Q Y,Liu J,Murugan A V,et al.High capacity doublelayer surface modified Li[Li0.2Mn0.54Ni0.13Co0.13]O2cathode with improved rate capability.J Mater Chem,2009,19(28):4965
[34]Lian F,Gao M,Ma L L,et al.The effect of surface modification on high capacity Li1.375Ni0.25Mn0.75O2+γcathode material for lithium-ion batteries.J Alloys Compd,2014,608:158
[35]Wu Y,Manthiram A.Effect of surface modifications on the layered solid solution cathodes(1-z)Li[Li1/3Mn2/3]O2-z Li[Mn0.5-yNi0.5-yCo2y]O2.Solid State Ionics,2009,180(1):50
[36]Jin Y C,Duh J G.Fluorination induced the surface segregation of high voltage spinel on lithium-rich layered cathodes for enhanced rate capability in lithium ion batteries.ACS Appl Mater Interfaces,2016,8(6):3883
[37]Kobayashi G,Irii Y,Matsumoto F,et al.Improving cycling performance of Li-rich layered cathode materials through combination of Al2O3-based surface modification and stepwise precycling.J Power Sources,2016,303:250
[38]Kim D H,Sandi G,Croy J R,et al.Composite‘layered-layered-spinel’cathode structures for lithium-ion batteries.J Electrochem Soc,2013,160(1):A31
[39]Luo D,Li G S,Fu C C,et al.A new spinel-layered Li-rich microsphere as a high-rate cathode material for Li-ion batteries.Adv Energy Mater,2014,4(11):1400062
[40]Bian X F,Fu Q,Qiu H L,et al.High-performance Li(Li0.18Ni0.15Co0.15Mn0.52)O2@Li4M5O12heterostructured cathode material coated with a lithium borate oxide glass layer.Chem Mater,2015,27(16):5745
[41]Zhao E Y,Liu X F,Hu Z B,et al.Facile synthesis and enhanced electrochemical performances of Li2Ti O3-coated lithiumrich layered Li1.13Ni0.30Mn0.57O2cathode materials for lithiumion batteries.J Power Sources,2015,294:141
[42]Jung Y S,Cavanagh A S,Yan Y F,et al.Effects of atomic layer deposition of Al2O3on the Li[Li0.20Mn0.54Ni0.13Co0.13]O2cathode for lithium-ion batteries.J Electrochem Soc,2011,158(12):A1298
[43]Liu H,Du C Y,Yin G P,et al.An Li-rich oxide cathode material with mosaic spinel grain and a surface coating for high performance Li-ion batteries.J Mater Chem A,2014,2(37):15640
[44]Wu F,Li N,Su Y F,et al.Ultrathin spinel membrane-encapsulated layered lithium-rich cathode material for advanced Li-ion batteries.Nano Lett,2014,14(6):3550
[45]Wu Y,Murugan A V,Manthiram A.Surface modification of high capacity layered Li[Li0.2Mn0.54Ni0.13Co0.13]O2cathodes by Al PO4.J Electrochem Soc,2008,155(9):A635