The increasing demand for energy storage requires energy storage devices to have greater capacity, and there are high hopes for lithium-ion batteries (LIBs) in the energy storage field. Their structural stability as cathode materials and their voltage profiles for insertion/extraction directly determine the specific energy and power densities of the battery system. In recent years, research related to these characteristics has remained the core issue in the LIB research field, particularly the characterization of the material structure and electrochemical behavior. Important real-time and in-situ strategies were employed in designing and developing more types of materials with excellent performance. For the cathode materials, detailed insights, such as their microstructure, chemical composition, ion valence and states, character of morphology, ion transport, and electron transfer, are beneficial in the preparation, structure design and modification of electrode materials. In this review, the operating principles, usage scenarios, and corresponding information of characterization techniques are introduced, and some examples that use these techniques to characterize LIB anode materials are listed. Finally, the advantages and disadvantages of current characterization techniques are compared, and the major challenges in research studies are discussed. Hence, this article summarizes the typically used technologies that are applied in monitoring the structural changes and surface-interface behaviors of cathode materials, including the microscopic imaging, phase analysis, composition and chemical valence, and bonding and functional groups to provide a reference for the combined utilization of various characterization technologies and to promote the development of an ideal electrode material.
MU Yue. Methods of investigating structural evolution and interface behavior in cathode materials for Li-ion batteries[J]. Energy Storage Science and Technology, 2021, 10(1): 7-26
Fig.2
Some cell setups used for in situ characterization[4-19]: (a) for AFM; (b), (c)for SEM; (d) for TEM; (e) for STEM; (f), (g) for Cryo-EM; (h), (i), (j) for X-ray characterization; (k), (l) for neutron characterization; (m) for XRD-CT; (n) for FTIR; (p) for EQCM
Fig.3
SEM images of GO, weight ratio of balls to GO aqueous suspension: (a) 0.6,; (b) 1.2[30]; (c) TEM image of LiMnPO4[31]; (d) HRTEM image of NCM-H[38]
SEM和TEM可以使用环境腔技术(environmental scanning electron microscopy,ESEM)实现原位观察。而原位观察需要在电池运行过程中使探测电子束进入电池体系,因此在电池设计上和传统电池差别很大。这一类技术目前没有在正极表征上进行使用,但在负极的研究中已经开始使用,例如,Zheng等[39]设计了一种原位电池,如图所示使用环境腔技术,然后Au针尖上固定直壁碳纳米管做正极,W针尖上固定Li做负极,另一W针尖用以划擦Li的表面,保证原始Li暴露出来,使用这个原位装置观察充放电循环时的结构演变。后续在正极材料,尤其是单晶结构正极材料的表面行为表征方面将会有潜在的应用前景。Unocic等[7]使用Poseiden 500原位微流体电化学S/TEM表征系统,如图4所示,此系统本质上是一个密封在TEM支架端的三电极微流体电化学电池。该支架集成了微流体输送系统和电气触点,能控制电解液的输送并进行实时的电化学测量。制作的微型器件以玻璃碳和铂微带为电极,并以SiNx作为观察窗口。
Fig.5
(a) HADDF-STEM image of LMR, showing structure of defect spinel structure with empty 16c octahedral sites[32]; (b) ABF-STEM image of processed Li2MnO3[33]; (c) AFM images of thin-film V2O5 cathodes on different states[34]
Fig.12
(a) XPS spectra of 3% LiAlO2 doped sample of Mn element; (b) is XPS spectra of sample in (a) after 100 cycles[67]; (c) Transition metal L-edge EELS spectra along scanning pathway[59]; (d) EDX image of Ti-doped LiNi0.5Mn1.5O4-δ[60]
Fig.15
(a) FTIR patterns of LRO electrode[17]; (b) Raman spectra of pristine and cycled Li1.2Ni0.16Mn0.56Co0.08O2[69]; (c) NMR shows effect of aluminum content on Al local structure of NCM 523[70]
NMR是使用频率为MHz级别的电磁波照射分子,使磁性原子核在外磁场中发生磁能级的共振跃迁,并获得吸收信号,得出一个射频辐射吸收的光谱。获得NMR信号需要核子数为奇数的原子。NMR具有高的能量和空间的分辨能力。此外基于NMR的核磁共振成像(NMRI)也在分析电池电极时使用[72]。NMR中的魔角旋转核磁共振谱(MAS NMR)可以定性、定量地表征Al的配位信息,分析其在晶格中的作用,这对NCA正极材料的研究来说很有意义。Dogan等[70]就使用27Al MAS NMR直接观察NCA正极材料中的Al晶格环境[图15(c)],得知对NCA而言,晶体中的Al更倾向于和6个Ni配位,成蜂巢状,而增加Co的含量会增加铝的位错。而Al含量增大会使铝酸盐增多,出现偏析倾向,同时分析得知NCA中Al的在晶格中的最大占有率约为5%。Yim等[71]使用硼酸三苯作为添加剂改善CEI性能,使用原位NMR分析硼酸三苯对残锂清除的影响,硼酸三苯参与反应的CEI层抑制了电解液的分解,从而增强了电极表面的稳定性。
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Some cell setups used for in situ characterization[4-19]: (a) for AFM; (b), (c)for SEM; (d) for TEM; (e) for STEM; (f), (g) for Cryo-EM; (h), (i), (j) for X-ray characterization; (k), (l) for neutron characterization; (m) for XRD-CT; (n) for FTIR; (p) for EQCMFig.2
(1)避免干扰和减少信号衰减 ...
... [4-19]: (a) for AFM; (b), (c)for SEM; (d) for TEM; (e) for STEM; (f), (g) for Cryo-EM; (h), (i), (j) for X-ray characterization; (k), (l) for neutron characterization; (m) for XRD-CT; (n) for FTIR; (p) for EQCMFig.2
... [17];(b) 循环前后对比的Li1.2Ni0.16Mn0.56Co0.08O2拉曼图谱[69];(c) 铝含量对NCM 523中铝的局部结构影响的NMR图谱[70](a) FTIR patterns of LRO electrode[17]; (b) Raman spectra of pristine and cycled Li1.2Ni0.16Mn0.56Co0.08O2[69]; (c) NMR shows effect of aluminum content on Al local structure of NCM 523[70]Fig.15
... [17]; (b) Raman spectra of pristine and cycled Li1.2Ni0.16Mn0.56Co0.08O2[69]; (c) NMR shows effect of aluminum content on Al local structure of NCM 523[70]Fig.15
Some cell setups used for in situ characterization[4-19]: (a) for AFM; (b), (c)for SEM; (d) for TEM; (e) for STEM; (f), (g) for Cryo-EM; (h), (i), (j) for X-ray characterization; (k), (l) for neutron characterization; (m) for XRD-CT; (n) for FTIR; (p) for EQCMFig.2
(1)避免干扰和减少信号衰减 ...
... -19]: (a) for AFM; (b), (c)for SEM; (d) for TEM; (e) for STEM; (f), (g) for Cryo-EM; (h), (i), (j) for X-ray characterization; (k), (l) for neutron characterization; (m) for XRD-CT; (n) for FTIR; (p) for EQCMFig.2
... [30];(c) LiMnPO4的TEM[31];(d) NCM-H的HRTEM[38]SEM images of GO, weight ratio of balls to GO aqueous suspension: (a) 0.6,; (b) 1.2[30]; (c) TEM image of LiMnPO4[31]; (d) HRTEM image of NCM-H[38]Fig.3
SEM和TEM可以使用环境腔技术(environmental scanning electron microscopy,ESEM)实现原位观察.而原位观察需要在电池运行过程中使探测电子束进入电池体系,因此在电池设计上和传统电池差别很大.这一类技术目前没有在正极表征上进行使用,但在负极的研究中已经开始使用,例如,Zheng等[39]设计了一种原位电池,如图所示使用环境腔技术,然后Au针尖上固定直壁碳纳米管做正极,W针尖上固定Li做负极,另一W针尖用以划擦Li的表面,保证原始Li暴露出来,使用这个原位装置观察充放电循环时的结构演变.后续在正极材料,尤其是单晶结构正极材料的表面行为表征方面将会有潜在的应用前景.Unocic等[7]使用Poseiden 500原位微流体电化学S/TEM表征系统,如图4所示,此系统本质上是一个密封在TEM支架端的三电极微流体电化学电池.该支架集成了微流体输送系统和电气触点,能控制电解液的输送并进行实时的电化学测量.制作的微型器件以玻璃碳和铂微带为电极,并以SiNx作为观察窗口. ...
... [30]; (c) TEM image of LiMnPO4[31]; (d) HRTEM image of NCM-H[38]Fig.3
SEM和TEM可以使用环境腔技术(environmental scanning electron microscopy,ESEM)实现原位观察.而原位观察需要在电池运行过程中使探测电子束进入电池体系,因此在电池设计上和传统电池差别很大.这一类技术目前没有在正极表征上进行使用,但在负极的研究中已经开始使用,例如,Zheng等[39]设计了一种原位电池,如图所示使用环境腔技术,然后Au针尖上固定直壁碳纳米管做正极,W针尖上固定Li做负极,另一W针尖用以划擦Li的表面,保证原始Li暴露出来,使用这个原位装置观察充放电循环时的结构演变.后续在正极材料,尤其是单晶结构正极材料的表面行为表征方面将会有潜在的应用前景.Unocic等[7]使用Poseiden 500原位微流体电化学S/TEM表征系统,如图4所示,此系统本质上是一个密封在TEM支架端的三电极微流体电化学电池.该支架集成了微流体输送系统和电气触点,能控制电解液的输送并进行实时的电化学测量.制作的微型器件以玻璃碳和铂微带为电极,并以SiNx作为观察窗口. ...
4
... Microimaging characterization in recent yearsTable 1
... [31];(d) NCM-H的HRTEM[38]SEM images of GO, weight ratio of balls to GO aqueous suspension: (a) 0.6,; (b) 1.2[30]; (c) TEM image of LiMnPO4[31]; (d) HRTEM image of NCM-H[38]Fig.3
SEM和TEM可以使用环境腔技术(environmental scanning electron microscopy,ESEM)实现原位观察.而原位观察需要在电池运行过程中使探测电子束进入电池体系,因此在电池设计上和传统电池差别很大.这一类技术目前没有在正极表征上进行使用,但在负极的研究中已经开始使用,例如,Zheng等[39]设计了一种原位电池,如图所示使用环境腔技术,然后Au针尖上固定直壁碳纳米管做正极,W针尖上固定Li做负极,另一W针尖用以划擦Li的表面,保证原始Li暴露出来,使用这个原位装置观察充放电循环时的结构演变.后续在正极材料,尤其是单晶结构正极材料的表面行为表征方面将会有潜在的应用前景.Unocic等[7]使用Poseiden 500原位微流体电化学S/TEM表征系统,如图4所示,此系统本质上是一个密封在TEM支架端的三电极微流体电化学电池.该支架集成了微流体输送系统和电气触点,能控制电解液的输送并进行实时的电化学测量.制作的微型器件以玻璃碳和铂微带为电极,并以SiNx作为观察窗口. ...
... [31]; (d) HRTEM image of NCM-H[38]Fig.3
SEM和TEM可以使用环境腔技术(environmental scanning electron microscopy,ESEM)实现原位观察.而原位观察需要在电池运行过程中使探测电子束进入电池体系,因此在电池设计上和传统电池差别很大.这一类技术目前没有在正极表征上进行使用,但在负极的研究中已经开始使用,例如,Zheng等[39]设计了一种原位电池,如图所示使用环境腔技术,然后Au针尖上固定直壁碳纳米管做正极,W针尖上固定Li做负极,另一W针尖用以划擦Li的表面,保证原始Li暴露出来,使用这个原位装置观察充放电循环时的结构演变.后续在正极材料,尤其是单晶结构正极材料的表面行为表征方面将会有潜在的应用前景.Unocic等[7]使用Poseiden 500原位微流体电化学S/TEM表征系统,如图4所示,此系统本质上是一个密封在TEM支架端的三电极微流体电化学电池.该支架集成了微流体输送系统和电气触点,能控制电解液的输送并进行实时的电化学测量.制作的微型器件以玻璃碳和铂微带为电极,并以SiNx作为观察窗口. ...
4
... Microimaging characterization in recent yearsTable 1
... [33];(c) 薄膜V2O5正极循环各阶段的AFM图像[34](a) HADDF-STEM image of LMR, showing structure of defect spinel structure with empty 16c octahedral sites[32]; (b) ABF-STEM image of processed Li2MnO3[33]; (c) AFM images of thin-film V2O5 cathodes on different states[34]Fig.51.3 原子力显微镜
(a) HADDF-STEM image of LMR, showing structure of defect spinel structure with empty 16c octahedral sites[32]; (b) ABF-STEM image of processed Li2MnO3[33]; (c) AFM images of thin-film V2O5 cathodes on different states[34]Fig.51.3 原子力显微镜
... [38]SEM images of GO, weight ratio of balls to GO aqueous suspension: (a) 0.6,; (b) 1.2[30]; (c) TEM image of LiMnPO4[31]; (d) HRTEM image of NCM-H[38]Fig.3
SEM和TEM可以使用环境腔技术(environmental scanning electron microscopy,ESEM)实现原位观察.而原位观察需要在电池运行过程中使探测电子束进入电池体系,因此在电池设计上和传统电池差别很大.这一类技术目前没有在正极表征上进行使用,但在负极的研究中已经开始使用,例如,Zheng等[39]设计了一种原位电池,如图所示使用环境腔技术,然后Au针尖上固定直壁碳纳米管做正极,W针尖上固定Li做负极,另一W针尖用以划擦Li的表面,保证原始Li暴露出来,使用这个原位装置观察充放电循环时的结构演变.后续在正极材料,尤其是单晶结构正极材料的表面行为表征方面将会有潜在的应用前景.Unocic等[7]使用Poseiden 500原位微流体电化学S/TEM表征系统,如图4所示,此系统本质上是一个密封在TEM支架端的三电极微流体电化学电池.该支架集成了微流体输送系统和电气触点,能控制电解液的输送并进行实时的电化学测量.制作的微型器件以玻璃碳和铂微带为电极,并以SiNx作为观察窗口. ...
... [38]Fig.3
SEM和TEM可以使用环境腔技术(environmental scanning electron microscopy,ESEM)实现原位观察.而原位观察需要在电池运行过程中使探测电子束进入电池体系,因此在电池设计上和传统电池差别很大.这一类技术目前没有在正极表征上进行使用,但在负极的研究中已经开始使用,例如,Zheng等[39]设计了一种原位电池,如图所示使用环境腔技术,然后Au针尖上固定直壁碳纳米管做正极,W针尖上固定Li做负极,另一W针尖用以划擦Li的表面,保证原始Li暴露出来,使用这个原位装置观察充放电循环时的结构演变.后续在正极材料,尤其是单晶结构正极材料的表面行为表征方面将会有潜在的应用前景.Unocic等[7]使用Poseiden 500原位微流体电化学S/TEM表征系统,如图4所示,此系统本质上是一个密封在TEM支架端的三电极微流体电化学电池.该支架集成了微流体输送系统和电气触点,能控制电解液的输送并进行实时的电化学测量.制作的微型器件以玻璃碳和铂微带为电极,并以SiNx作为观察窗口. ...
3
... SEM和TEM可以使用环境腔技术(environmental scanning electron microscopy,ESEM)实现原位观察.而原位观察需要在电池运行过程中使探测电子束进入电池体系,因此在电池设计上和传统电池差别很大.这一类技术目前没有在正极表征上进行使用,但在负极的研究中已经开始使用,例如,Zheng等[39]设计了一种原位电池,如图所示使用环境腔技术,然后Au针尖上固定直壁碳纳米管做正极,W针尖上固定Li做负极,另一W针尖用以划擦Li的表面,保证原始Li暴露出来,使用这个原位装置观察充放电循环时的结构演变.后续在正极材料,尤其是单晶结构正极材料的表面行为表征方面将会有潜在的应用前景.Unocic等[7]使用Poseiden 500原位微流体电化学S/TEM表征系统,如图4所示,此系统本质上是一个密封在TEM支架端的三电极微流体电化学电池.该支架集成了微流体输送系统和电气触点,能控制电解液的输送并进行实时的电化学测量.制作的微型器件以玻璃碳和铂微带为电极,并以SiNx作为观察窗口. ...
... [39];(b) TEM原位电池装置[7](a) cell setup for in situ SEM[39]; (b) cell setup for TEM[7]Fig.41.2 扫描透射电子显微镜
(a) XRD image of pristine NCM622 and Zr-doped material[48]; (b) Rietveld refinement of high-resolution neutron diffraction patterns of discharged battery[50]Fig.7
(a) XPS spectra of 3% LiAlO2 doped sample of Mn element; (b) is XPS spectra of sample in (a) after 100 cycles[67]; (c) Transition metal L-edge EELS spectra along scanning pathway[59]; (d) EDX image of Ti-doped LiNi0.5Mn1.5O4-δ[60]Fig.12
(a) XPS spectra of 3% LiAlO2 doped sample of Mn element; (b) is XPS spectra of sample in (a) after 100 cycles[67]; (c) Transition metal L-edge EELS spectra along scanning pathway[59]; (d) EDX image of Ti-doped LiNi0.5Mn1.5O4-δ[60]Fig.12
... [67];(c) 沿扫描路径的过渡金属L边EELS谱[59];(d) Ti掺杂表面改性LiNi0.5Mn1.5O4-δ的EDX图像[60](a) XPS spectra of 3% LiAlO2 doped sample of Mn element; (b) is XPS spectra of sample in (a) after 100 cycles[67]; (c) Transition metal L-edge EELS spectra along scanning pathway[59]; (d) EDX image of Ti-doped LiNi0.5Mn1.5O4-δ[60]Fig.12
(a) FTIR patterns of LRO electrode[17]; (b) Raman spectra of pristine and cycled Li1.2Ni0.16Mn0.56Co0.08O2[69]; (c) NMR shows effect of aluminum content on Al local structure of NCM 523[70]Fig.15
(a) FTIR patterns of LRO electrode[17]; (b) Raman spectra of pristine and cycled Li1.2Ni0.16Mn0.56Co0.08O2[69]; (c) NMR shows effect of aluminum content on Al local structure of NCM 523[70]Fig.15