The rapid development of electric vehicle (EV) and hybrid electric vehicle (HEV) has put forward higher requirements on the energy density and cycle life of lithium-ion batteries. Cathode material is one of the most critical parts in determining the performance of lithium-ion batteries. Lithium-rich manganese-based layered oxides (LMLOs) are considered to be the most promising cathode materials for next-generation power batteries due to their high specific capacity (>250 mA·h/g), high work voltage, low cost and high safety. However, low initial coulombic efficiency, severe voltage fading, and poor cycle and rate performance prevent their practical application. This review summarizes the causes of the above-mentioned problems, including irreversible oxygen release, irreversible transformation from layered structure to spinel phase, and migration and valence change of transition metal ions. What’s more, some typical solutions reported by domestic and overseas researchers in recent years are also summarized from the following four aspects: surface coating, surface/bulk doping, crystal-facet control, and surface integrated structure, respectively.
ZHANG Zuhao. Challenges and solutions of lithium-rich manganese-based layered oxide cathode materials[J]. Energy Storage Science and Technology, 2021, 10(2): 408-424
Fig. 1
The Crystal structure of the (a) LiMO2(Rm)、(b)Li2MnO3(C2/m) viewed from the [100] crystallographic direction[36]; (c) STEM-HAADF image of the 45 cycled Li1.2Ni0.2Mn0.6O2[37]; (d) Schematic diagram showing the charge/discharge curves of a typical LMLOs with the evolution of structure during cycling[43]
Fig. 2
(a) the first charge-discharge curve of Li1.2Mn0.6Ni0.2O2[46]; (b) the first cycle voltage profiles and gas evolution rates of Li1.2Mn0.6Ni0.2O2 electrode[46]; (c) schematic of gas-solid interface reaction (GSIR) between Li-rich layered oxides and carbon dioxide[30]
Fig. 3
(a) schematic describing the TM migration mechanism in Li1.2Ni0.2Ru0.6O2 upon cycling, where blue and orange indicate transition metal and lithium ions, respectively[53]; (b) schematic view of structural transformation from layered to spinel phase upon cycling for Li1.2Ni0.2Mn0.6O2 active materials[14]
Fig. 4
Redox couple evolution of Li1.2Ni0.15Co0.1Mn0.55O2 during cycling[15]. (a) the contribution towards the discharge capacity from Ni, Co, Mn and O redox at various cycles; (b) effects of electronic structure changeon the Fermi level; (c) diagram of the correlation between redox couple and energy level of each element
Fig. 5
(a) magnitude of the Fourier transformed Mn K-edge spectra of Li1.2Ni0.15Co0.1Mn0.55O2 collected during 5 V constant voltage charging[16]; (b) projection view of the corresponding Ni-O, Co-O, and Mn-O peak magnitudes of the Fourier transformed K-edge spectra as functions of charging time[16]; (c) the dQ/dV curves of cathode material Li[Li0.2Ni0.2Mn0.6]O2 at various current density[18]
Fig. 6
(a) the TEM image of the AlF3 coating on Li1.2Ni0.15Co0.10Mn0.55O2[64]; (b) higher magnification TEM image showing the AlF3 coating layer on the LMR cathode[64] ; (c) corresponding charging and discharging curve of uncoated material and AlF3-coated material during cycling[64]; (d) the mechanism of LSM-coated LM[65], (e) schematic of structure evolution of pristine LM and LSM-coated sample during electrochemical cycling[65]
Fig. 7
Schematic diagrams of the phase evolution routes for (a) pristine sample and (b) potassium-doped (V1, V2 and V3 stand for vacancies in lithium layer; Vt stands for tetrahedral vacancy and Vo for octahedral vacancy) [75]
Fig. 8
(a) the schematic process of surface doping and the Nb-enhanced surface structure[80]; (b) the EDS mapping of Mn and Nb for the LMR-Nb sample[80];(c) Schematic illustration of the structure design of gradient surface Na+ doping Li-rich material[82]; (d) The rate performance of pristine Li-rich material (PLR) and Na+ doped Li-rich material (SLR) [82]
Fig. 9
(a) schematic illustration of two kinds of nanoplates and the microstructure of their surfaces[84]; (b) schematic illustration of Li1.2Mn0.6Ni0.2O2[86] ; (c) SEM image of hierarchical Li1.2Mn0.54Ni0.13Co0.13O2 spheres[87]; (d) cycling performance of LMLOs at 2C, inset is the average voltage plots upon cycling at 2C[26]
Fig. 10
(a)~(b) in situ XRD image of LMLOs which before and after modification[90]; (c) high-resolution transmission electron miscroscopy (HRTEM) image of the layered@spinel@carbon heterostructure in LMLOs [32]; (d) schematic view of the layered@spinel@carbon heterostructure[32]; (e) schematic diagram of the formation process and design strategy of Li-rich layered oxide particle with phase gradient outer layer accompanied by poor nickel content[91]
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... [15]:(a) 在不同循环周期时,镍、钴、锰和氧元素对放电比容量的贡献;(b) 电子结构变化对费米能级的影响;(c) 每个元素的能级与氧化还原电对的关系图Redox couple evolution of Li1.2Ni0.15Co0.1Mn0.55O2 during cycling[15]. (a) the contribution towards the discharge capacity from Ni, Co, Mn and O redox at various cycles; (b) effects of electronic structure changeon the Fermi level; (c) diagram of the correlation between redox couple and energy level of each elementFig. 42.3 倍率性能差
... [15]. (a) the contribution towards the discharge capacity from Ni, Co, Mn and O redox at various cycles; (b) effects of electronic structure changeon the Fermi level; (c) diagram of the correlation between redox couple and energy level of each elementFig. 42.3 倍率性能差
... [16];(b) 傅里叶变换K-edge光谱对应的Ni-O,Co-O和Mn-O峰值幅度随充电时间变化的投影图[16];(c) 正极材料Li[Li0.2Ni0.2Mn0.6]O2在不同电流密度下对应的dQ/dV曲线[18](a) magnitude of the Fourier transformed Mn K-edge spectra of Li1.2Ni0.15Co0.1Mn0.55O2 collected during 5 V constant voltage charging[16]; (b) projection view of the corresponding Ni-O, Co-O, and Mn-O peak magnitudes of the Fourier transformed K-edge spectra as functions of charging time[16]; (c) the dQ/dV curves of cathode material Li[Li0.2Ni0.2Mn0.6]O2 at various current density[18]Fig. 53 解决方法3.1 包 覆
... [16];(c) 正极材料Li[Li0.2Ni0.2Mn0.6]O2在不同电流密度下对应的dQ/dV曲线[18](a) magnitude of the Fourier transformed Mn K-edge spectra of Li1.2Ni0.15Co0.1Mn0.55O2 collected during 5 V constant voltage charging[16]; (b) projection view of the corresponding Ni-O, Co-O, and Mn-O peak magnitudes of the Fourier transformed K-edge spectra as functions of charging time[16]; (c) the dQ/dV curves of cathode material Li[Li0.2Ni0.2Mn0.6]O2 at various current density[18]Fig. 53 解决方法3.1 包 覆
... [16]; (b) projection view of the corresponding Ni-O, Co-O, and Mn-O peak magnitudes of the Fourier transformed K-edge spectra as functions of charging time[16]; (c) the dQ/dV curves of cathode material Li[Li0.2Ni0.2Mn0.6]O2 at various current density[18]Fig. 53 解决方法3.1 包 覆
... [18](a) magnitude of the Fourier transformed Mn K-edge spectra of Li1.2Ni0.15Co0.1Mn0.55O2 collected during 5 V constant voltage charging[16]; (b) projection view of the corresponding Ni-O, Co-O, and Mn-O peak magnitudes of the Fourier transformed K-edge spectra as functions of charging time[16]; (c) the dQ/dV curves of cathode material Li[Li0.2Ni0.2Mn0.6]O2 at various current density[18]Fig. 53 解决方法3.1 包 覆
... [26](a) schematic illustration of two kinds of nanoplates and the microstructure of their surfaces[84]; (b) schematic illustration of Li1.2Mn0.6Ni0.2O2[86] ; (c) SEM image of hierarchical Li1.2Mn0.54Ni0.13Co0.13O2 spheres[87]; (d) cycling performance of LMLOs at 2C, inset is the average voltage plots upon cycling at 2C[26]Fig. 93.4 表面集成结构
... [30](a) the first charge-discharge curve of Li1.2Mn0.6Ni0.2O2[46]; (b) the first cycle voltage profiles and gas evolution rates of Li1.2Mn0.6Ni0.2O2 electrode[46]; (c) schematic of gas-solid interface reaction (GSIR) between Li-rich layered oxides and carbon dioxide[30]Fig. 22.2 容量和电压衰减
... [32];(d)层状@尖晶石@碳异质结构示意图[32];(e)外层为相梯度且镍含量较低的富锂层状氧化物颗粒形成过程及设计策略示意图[91](a)~(b) in situ XRD image of LMLOs which before and after modification[90]; (c) high-resolution transmission electron miscroscopy (HRTEM) image of the layered@spinel@carbon heterostructure in LMLOs [32]; (d) schematic view of the layered@spinel@carbon heterostructure[32]; (e) schematic diagram of the formation process and design strategy of Li-rich layered oxide particle with phase gradient outer layer accompanied by poor nickel content[91]Fig. 10
... [32];(e)外层为相梯度且镍含量较低的富锂层状氧化物颗粒形成过程及设计策略示意图[91](a)~(b) in situ XRD image of LMLOs which before and after modification[90]; (c) high-resolution transmission electron miscroscopy (HRTEM) image of the layered@spinel@carbon heterostructure in LMLOs [32]; (d) schematic view of the layered@spinel@carbon heterostructure[32]; (e) schematic diagram of the formation process and design strategy of Li-rich layered oxide particle with phase gradient outer layer accompanied by poor nickel content[91]Fig. 10
... [32]; (d) schematic view of the layered@spinel@carbon heterostructure[32]; (e) schematic diagram of the formation process and design strategy of Li-rich layered oxide particle with phase gradient outer layer accompanied by poor nickel content[91]Fig. 10
... [32]; (e) schematic diagram of the formation process and design strategy of Li-rich layered oxide particle with phase gradient outer layer accompanied by poor nickel content[91]Fig. 10
... [36];(c) Li1.2Ni0.2Mn0.6O2循环45次后的高角环形暗场-扫描透射显微镜(STEM-HAADF)图[37];(d) 典型LMLOs的充电/放电曲线以及循环过程中结构的演变示意图[43]The Crystal structure of the (a) LiMO2(Rm)、(b)Li2MnO3(C2/m) viewed from the [100] crystallographic direction[36]; (c) STEM-HAADF image of the 45 cycled Li1.2Ni0.2Mn0.6O2[37]; (d) Schematic diagram showing the charge/discharge curves of a typical LMLOs with the evolution of structure during cycling[43]Fig. 1
... [36]; (c) STEM-HAADF image of the 45 cycled Li1.2Ni0.2Mn0.6O2[37]; (d) Schematic diagram showing the charge/discharge curves of a typical LMLOs with the evolution of structure during cycling[43]Fig. 1
The Crystal structure of the (a) LiMO2(Rm)、(b)Li2MnO3(C2/m) viewed from the [100] crystallographic direction[36]; (c) STEM-HAADF image of the 45 cycled Li1.2Ni0.2Mn0.6O2[37]; (d) Schematic diagram showing the charge/discharge curves of a typical LMLOs with the evolution of structure during cycling[43]Fig. 1
The Crystal structure of the (a) LiMO2(Rm)、(b)Li2MnO3(C2/m) viewed from the [100] crystallographic direction[36]; (c) STEM-HAADF image of the 45 cycled Li1.2Ni0.2Mn0.6O2[37]; (d) Schematic diagram showing the charge/discharge curves of a typical LMLOs with the evolution of structure during cycling[43]Fig. 1
... [46];(b)首次循环时Li1.2Ni0.2Mn0.6O2的电压分布和气体生成速率[46];(c) 富锂层状氧化物与CO2之间的气固界面反应(GSIR)原理图[30](a) the first charge-discharge curve of Li1.2Mn0.6Ni0.2O2[46]; (b) the first cycle voltage profiles and gas evolution rates of Li1.2Mn0.6Ni0.2O2 electrode[46]; (c) schematic of gas-solid interface reaction (GSIR) between Li-rich layered oxides and carbon dioxide[30]Fig. 22.2 容量和电压衰减
... [46];(c) 富锂层状氧化物与CO2之间的气固界面反应(GSIR)原理图[30](a) the first charge-discharge curve of Li1.2Mn0.6Ni0.2O2[46]; (b) the first cycle voltage profiles and gas evolution rates of Li1.2Mn0.6Ni0.2O2 electrode[46]; (c) schematic of gas-solid interface reaction (GSIR) between Li-rich layered oxides and carbon dioxide[30]Fig. 22.2 容量和电压衰减
... [46]; (b) the first cycle voltage profiles and gas evolution rates of Li1.2Mn0.6Ni0.2O2 electrode[46]; (c) schematic of gas-solid interface reaction (GSIR) between Li-rich layered oxides and carbon dioxide[30]Fig. 22.2 容量和电压衰减
... (b) Li1.2Ni0.2Mn0.6O2材料在循环过程中从层状到尖晶石相的结构转变示意图[14](a) schematic describing the TM migration mechanism in Li1.2Ni0.2Ru0.6O2 upon cycling, where blue and orange indicate transition metal and lithium ions, respectively[53]; (b) schematic view of structural transformation from layered to spinel phase upon cycling for Li1.2Ni0.2Mn0.6O2 active materials[14]Fig. 3
... [64];(b) 高倍数下的TEM图像所显示出LMR阴极上的AlF3涂层[64];(c) 未包覆材料和AlF3包覆材料在循环过程中的充放电曲线[64];(d) LSM包覆LM的机理[65]; (e) LM原样和LSM包覆样在电化学循环过程中的结构演变示意图[65](a) the TEM image of the AlF3 coating on Li1.2Ni0.15Co0.10Mn0.55O2[64]; (b) higher magnification TEM image showing the AlF3 coating layer on the LMR cathode[64] ; (c) corresponding charging and discharging curve of uncoated material and AlF3-coated material during cycling[64]; (d) the mechanism of LSM-coated LM[65], (e) schematic of structure evolution of pristine LM and LSM-coated sample during electrochemical cycling[65]Fig. 63.2 掺 杂
... [64];(c) 未包覆材料和AlF3包覆材料在循环过程中的充放电曲线[64];(d) LSM包覆LM的机理[65]; (e) LM原样和LSM包覆样在电化学循环过程中的结构演变示意图[65](a) the TEM image of the AlF3 coating on Li1.2Ni0.15Co0.10Mn0.55O2[64]; (b) higher magnification TEM image showing the AlF3 coating layer on the LMR cathode[64] ; (c) corresponding charging and discharging curve of uncoated material and AlF3-coated material during cycling[64]; (d) the mechanism of LSM-coated LM[65], (e) schematic of structure evolution of pristine LM and LSM-coated sample during electrochemical cycling[65]Fig. 63.2 掺 杂
... [64];(d) LSM包覆LM的机理[65]; (e) LM原样和LSM包覆样在电化学循环过程中的结构演变示意图[65](a) the TEM image of the AlF3 coating on Li1.2Ni0.15Co0.10Mn0.55O2[64]; (b) higher magnification TEM image showing the AlF3 coating layer on the LMR cathode[64] ; (c) corresponding charging and discharging curve of uncoated material and AlF3-coated material during cycling[64]; (d) the mechanism of LSM-coated LM[65], (e) schematic of structure evolution of pristine LM and LSM-coated sample during electrochemical cycling[65]Fig. 63.2 掺 杂
... [64]; (b) higher magnification TEM image showing the AlF3 coating layer on the LMR cathode[64] ; (c) corresponding charging and discharging curve of uncoated material and AlF3-coated material during cycling[64]; (d) the mechanism of LSM-coated LM[65], (e) schematic of structure evolution of pristine LM and LSM-coated sample during electrochemical cycling[65]Fig. 63.2 掺 杂
... [64] ; (c) corresponding charging and discharging curve of uncoated material and AlF3-coated material during cycling[64]; (d) the mechanism of LSM-coated LM[65], (e) schematic of structure evolution of pristine LM and LSM-coated sample during electrochemical cycling[65]Fig. 63.2 掺 杂
... [64]; (d) the mechanism of LSM-coated LM[65], (e) schematic of structure evolution of pristine LM and LSM-coated sample during electrochemical cycling[65]Fig. 63.2 掺 杂
... [65]; (e) LM原样和LSM包覆样在电化学循环过程中的结构演变示意图[65](a) the TEM image of the AlF3 coating on Li1.2Ni0.15Co0.10Mn0.55O2[64]; (b) higher magnification TEM image showing the AlF3 coating layer on the LMR cathode[64] ; (c) corresponding charging and discharging curve of uncoated material and AlF3-coated material during cycling[64]; (d) the mechanism of LSM-coated LM[65], (e) schematic of structure evolution of pristine LM and LSM-coated sample during electrochemical cycling[65]Fig. 63.2 掺 杂
... [65](a) the TEM image of the AlF3 coating on Li1.2Ni0.15Co0.10Mn0.55O2[64]; (b) higher magnification TEM image showing the AlF3 coating layer on the LMR cathode[64] ; (c) corresponding charging and discharging curve of uncoated material and AlF3-coated material during cycling[64]; (d) the mechanism of LSM-coated LM[65], (e) schematic of structure evolution of pristine LM and LSM-coated sample during electrochemical cycling[65]Fig. 63.2 掺 杂
... [75]Schematic diagrams of the phase evolution routes for (a) pristine sample and (b) potassium-doped (V1, V2 and V3 stand for vacancies in lithium layer; Vt stands for tetrahedral vacancy and Vo for octahedral vacancy) [75]Fig. 73.2.2 表面掺杂
... [80];(b) 表面掺杂和Nb增强表面结构的示意图[80];(c) 梯度表面Na+掺杂富锂材料的结构设计示意图[82];(d) 富锂原始样品(PLR)和Na+掺杂的样品(SLR)的倍率性能[82](a) the schematic process of surface doping and the Nb-enhanced surface structure[80]; (b) the EDS mapping of Mn and Nb for the LMR-Nb sample[80];(c) Schematic illustration of the structure design of gradient surface Na+ doping Li-rich material[82]; (d) The rate performance of pristine Li-rich material (PLR) and Na+ doped Li-rich material (SLR) [82]Fig. 83.3 晶面调控
... [80];(c) 梯度表面Na+掺杂富锂材料的结构设计示意图[82];(d) 富锂原始样品(PLR)和Na+掺杂的样品(SLR)的倍率性能[82](a) the schematic process of surface doping and the Nb-enhanced surface structure[80]; (b) the EDS mapping of Mn and Nb for the LMR-Nb sample[80];(c) Schematic illustration of the structure design of gradient surface Na+ doping Li-rich material[82]; (d) The rate performance of pristine Li-rich material (PLR) and Na+ doped Li-rich material (SLR) [82]Fig. 83.3 晶面调控
... [80]; (b) the EDS mapping of Mn and Nb for the LMR-Nb sample[80];(c) Schematic illustration of the structure design of gradient surface Na+ doping Li-rich material[82]; (d) The rate performance of pristine Li-rich material (PLR) and Na+ doped Li-rich material (SLR) [82]Fig. 83.3 晶面调控
... [80];(c) Schematic illustration of the structure design of gradient surface Na+ doping Li-rich material[82]; (d) The rate performance of pristine Li-rich material (PLR) and Na+ doped Li-rich material (SLR) [82]Fig. 83.3 晶面调控
... [82];(d) 富锂原始样品(PLR)和Na+掺杂的样品(SLR)的倍率性能[82](a) the schematic process of surface doping and the Nb-enhanced surface structure[80]; (b) the EDS mapping of Mn and Nb for the LMR-Nb sample[80];(c) Schematic illustration of the structure design of gradient surface Na+ doping Li-rich material[82]; (d) The rate performance of pristine Li-rich material (PLR) and Na+ doped Li-rich material (SLR) [82]Fig. 83.3 晶面调控
... [82](a) the schematic process of surface doping and the Nb-enhanced surface structure[80]; (b) the EDS mapping of Mn and Nb for the LMR-Nb sample[80];(c) Schematic illustration of the structure design of gradient surface Na+ doping Li-rich material[82]; (d) The rate performance of pristine Li-rich material (PLR) and Na+ doped Li-rich material (SLR) [82]Fig. 83.3 晶面调控
... [84];(b) Li1.2Mn0.6Ni0.2O2的示意图[86];(c) 分层Li1.2Mn0.54Ni0.13Co0.13O2球体的SEM图像[87];(d) LMLOs在2C时的循环性能,插图为2C循环时的平均电压图[26](a) schematic illustration of two kinds of nanoplates and the microstructure of their surfaces[84]; (b) schematic illustration of Li1.2Mn0.6Ni0.2O2[86] ; (c) SEM image of hierarchical Li1.2Mn0.54Ni0.13Co0.13O2 spheres[87]; (d) cycling performance of LMLOs at 2C, inset is the average voltage plots upon cycling at 2C[26]Fig. 93.4 表面集成结构
... [84]; (b) schematic illustration of Li1.2Mn0.6Ni0.2O2[86] ; (c) SEM image of hierarchical Li1.2Mn0.54Ni0.13Co0.13O2 spheres[87]; (d) cycling performance of LMLOs at 2C, inset is the average voltage plots upon cycling at 2C[26]Fig. 93.4 表面集成结构
... [86];(c) 分层Li1.2Mn0.54Ni0.13Co0.13O2球体的SEM图像[87];(d) LMLOs在2C时的循环性能,插图为2C循环时的平均电压图[26](a) schematic illustration of two kinds of nanoplates and the microstructure of their surfaces[84]; (b) schematic illustration of Li1.2Mn0.6Ni0.2O2[86] ; (c) SEM image of hierarchical Li1.2Mn0.54Ni0.13Co0.13O2 spheres[87]; (d) cycling performance of LMLOs at 2C, inset is the average voltage plots upon cycling at 2C[26]Fig. 93.4 表面集成结构
... [86] ; (c) SEM image of hierarchical Li1.2Mn0.54Ni0.13Co0.13O2 spheres[87]; (d) cycling performance of LMLOs at 2C, inset is the average voltage plots upon cycling at 2C[26]Fig. 93.4 表面集成结构
... [87];(d) LMLOs在2C时的循环性能,插图为2C循环时的平均电压图[26](a) schematic illustration of two kinds of nanoplates and the microstructure of their surfaces[84]; (b) schematic illustration of Li1.2Mn0.6Ni0.2O2[86] ; (c) SEM image of hierarchical Li1.2Mn0.54Ni0.13Co0.13O2 spheres[87]; (d) cycling performance of LMLOs at 2C, inset is the average voltage plots upon cycling at 2C[26]Fig. 93.4 表面集成结构
... [90];(c) LMLOs中层状@尖晶石@碳异质结构的高分辨率透射电子显微镜(HRTEM)图像[32];(d)层状@尖晶石@碳异质结构示意图[32];(e)外层为相梯度且镍含量较低的富锂层状氧化物颗粒形成过程及设计策略示意图[91](a)~(b) in situ XRD image of LMLOs which before and after modification[90]; (c) high-resolution transmission electron miscroscopy (HRTEM) image of the layered@spinel@carbon heterostructure in LMLOs [32]; (d) schematic view of the layered@spinel@carbon heterostructure[32]; (e) schematic diagram of the formation process and design strategy of Li-rich layered oxide particle with phase gradient outer layer accompanied by poor nickel content[91]Fig. 10
... [90]; (c) high-resolution transmission electron miscroscopy (HRTEM) image of the layered@spinel@carbon heterostructure in LMLOs [32]; (d) schematic view of the layered@spinel@carbon heterostructure[32]; (e) schematic diagram of the formation process and design strategy of Li-rich layered oxide particle with phase gradient outer layer accompanied by poor nickel content[91]Fig. 10
... [91](a)~(b) in situ XRD image of LMLOs which before and after modification[90]; (c) high-resolution transmission electron miscroscopy (HRTEM) image of the layered@spinel@carbon heterostructure in LMLOs [32]; (d) schematic view of the layered@spinel@carbon heterostructure[32]; (e) schematic diagram of the formation process and design strategy of Li-rich layered oxide particle with phase gradient outer layer accompanied by poor nickel content[91]Fig. 10