Investigation and improvement on the electrochemical performance and storage characteristics of LiNiO2-based materials for lithium ion battery

Zheng, Xiaobo; Li, Xinhai; Wang, Zhixing; Guo, Huajun; Huang, Zhenjun; Yan, Guochun; Wang, Ding

doi:10.1016/j.electacta.2016.01.142

Cited by 138 publications

(135 citation statements)

References 34 publications

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“…[13][14][15][16][17][18]23 In some studies, in addition to the XRD pattern of the parent material, poorly resolved Bragg peaks from a cubic phase were observed, which was attributed either to LiNi 2 O 4 spinel 13,14 28 Most authors, however, suggest that such cation exchange plays a minor role if any at all, favoring instead a redox process that is fully analogous to the one occurring in electrochemical delithiation. In this favored scenario, both Li + cations and oxygen atoms (referred to as "active oxygen species") 16,17 migrate toward the surface and combine with water and CO 2 to yield LiOH, LiHCO 3, and Li 2 CO 3, while Ni 3+ ions are reduced to Ni 2+ .…”

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confidence: 99%

“…14,15 As the material delithiates, repulsion between the oxygen layers increases and the lattice expands along the crystallographic c axis (that is orthogonal to the TM-O planes). [13][14][15][16][17][18]23 In some studies, in addition to the XRD pattern of the parent material, poorly resolved Bragg peaks from a cubic phase were observed, which was attributed either to LiNi 2 O 4 spinel 13,14 or (possibly, lithiated) NiO rock salt. 22 These chemical transformations in (and on) the oxide have been attributed 24 to a combination of redox and cation exchange processes.…”

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confidence: 99%

“…The presence of Ni 2+ at the surface is hinted by changes in the shape of Ni 2p 3/2 absorption band against the Ni 3+ background as observed in X-ray photoemission spectra (XPS). 13,16 However, insufficient spectral resolution makes this attribution somewhat uncertain.In recent years there has been a shift to processing of electrodes using aqueous slurries containing water-based polymer binders. Such processing is particularly common for silicon and silicon-graphite electrodes, as the traditional fluoropolymer binders are inadequate …”

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confidence: 99%

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“…Electrochemical extraction is not the only mechanism for oxide delithiation: exposure to liquid water, 11,12 moist air [13][14][15][16][17][18][19][20] and carbon dioxide gas 21,22 during synthesis and/or storage of the NCM material under the ambient conditions also causes loss of lithium ions. In air and CO 2 , the formation of lithium (bi)carbonate and hydroxide coatings on z E-mail: abraham@anl.gov oxide surfaces has been reported.…”

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Chemical Weathering of Layered Ni-Rich Oxide Electrode Materials: Evidence for Cation Exchange

Shkrob

Gilbert

Phillips

et al. 2017

J. Electrochem. Soc.

153

160

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Lithiated ternary oxides containing nickel, cobalt, and manganese are intercalation compounds that are used as positive electrodes in high-energy lithium-ion batteries. These oxides undergo changes, when they are stored in humid air or exposed to moisture, that adversely affect their electrochemical performance. There is a new urgency to better understanding of these "weathering" mechanisms as manufacturing moves toward a more environmentally benign aqueous processing of the positive electrode. Delithiation of the oxide and the formation of lithium salts (such as hydroxides and carbonates) coating the surface, are known to occur during moisture exposure. The redox reactions which follow this delithiation are believed to trigger all the other transformations. In this article we suggest another possibility: namely, the proton -lithium exchange. We argue that this hypothesis provides a simple, comprehensive rationale for our observations, which include contraction of the c-axis (unit cell) lattice parameter, rock salt phase formation in the subsurface regions, presence of amorphous surface films, and the partial recovery of oxide capacity during electrochemical relithiation. The detrimental effects of water exposure need to be mitigated before aqueous processing of the positive electrode can find widespread adoption during cell manufacturing. Improving the performance of lithium-ion batteries (LIBs) for electrically powered vehicles gives urgency to the development of high-capacity, high-voltage electrode materials, and layered Ni-rich oxides are presently among the most technological advanced materials that allow operation above +4.0 V vs Li + /Li. 1 Such materials (also known as NCMxyz materials) have the general composition of LiNi x/10 Co y/10 Mn z/10 O 2 , where x+y+z = 10. In these ternary oxides, the manganese stays in the Mn 4+ state during cell cycling, and the capacity mainly originates from the Ni 2+ /Ni 3+ and Ni 3+ /Ni 4+ redox couples. The monolayers of octahedra containing transition metal (TM) ions form a structural scaffold with the layers of mobile Li + ions placed in between. The crystalline material retains the structure of the progenitor material of the family, viz. α-LiCoO 2 , 2 with the unit cell belonging to the rhombohedral R(-3)m space group. During electrochemical cycling, the lithium ions intercalate into (and deintercalate from) the layered crystals as the redox state of (mainly the) nickel ions changes to provide the overall charge neutrality.In this study, we examine one such material, NCM523, which represents a particular trade-off between the cycling rate (that improves with Co content), safety (that improves with Mn content), and capacity (that increases with Ni content).1 The safety concerns mainly relate to the thermal and chemical stability, including oxidation of the organic electrolyte by catalytic centers at the oxide surface 3 and phase transitions in the delithiated material that occur when a significant fraction of nickel ions is reduced to Ni 2+ ions and molecular oxygen ...

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confidence: 99%

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confidence: 99%

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confidence: 99%

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confidence: 99%

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confidence: 99%

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Chemical Weathering of Layered Ni-Rich Oxide Electrode Materials: Evidence for Cation Exchange

Shkrob

Gilbert

Phillips

et al. 2017

J. Electrochem. Soc.

153

160

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Cooling Induced Surface Reconstruction during Synthesis of High‐Ni Layered Oxides

Zhang

et al. 2019

Advanced Energy Materials

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Li-ion batteries (LIBs) are now increasingly used in electric vehicles (EVs) and other large-scale applications, but a bottleneck for their mass adoption is low Li-storage capacity, which is largely constrained by cathodes, typically with a gravimetric capacity equivalent to ≈1/2 that of the graphite anode. Despite much research into candidate cathodes for LIBs, transition metal (TM) layered oxides with a hexagonal structure (space group R3m) have remained dominant over the past three decades. [1,2] In particular, high-Ni layered oxides, LiNi x Mn y Co z O 2 (NMC; x ≥ 0.7) are now attracting world-wide interest for their high theoretical capacity (≈280 mA h g −1 ), which, however, has been difficult to realize due to the issues associated with high Ni loading: [3][4][5][6][7][8] in addition to cationic disordering (Li/Ni mixing) and the resulted low electrochemical activity, [9][10][11] Transition metal layered oxides have been the dominant cathodes in lithiumion batteries, and among them, high-Ni ones (LiNi x Mn y Co z O 2 ; x ≥ 0.7) with greatly boosted capacity and reduced cost are of particular interest for largescale applications. The high Ni loading, on the other hand, raises the critical issues of surface instability and poor rate performance. The rational design of synthesis leading to layered LiNi 0.7 Mn 0.15 Co 0.15 O 2 with greatly enhanced rate capability is demonstrated, by implementing a quenching process alternative to the general slow cooling. In situ synchrotron X-ray diffraction, coupled with surface analysis, is applied to studies of the synthesis process, revealing cooling-induced surface reconstruction involving Li 2 CO 3 accumulation, formation of a Li-deficient layer and Ni reduction at the particle surface. The reconstruction process occurs predominantly at high temperatures (above 350 °C) and is highly cooling-rate dependent, implying that surface reconstruction can be suppressed through synthetic control, i.e., quenching to improve the surface stability and rate performance of the synthesized materials. These findings may provide guidance to rational synthesis of high-Ni cathode materials. (2 of 10)cycling stability and safety are often compromised due to the surface-related issues. [12][13][14][15] Significant efforts in developing high-Ni NMC cathodes have been put on studying electrochemical impact, origin of the Li/ Ni disordering, and on improving Li/Ni ordering through optimizing synthesis conditions. [9,11,16,17] It is until very recently that people started to pay close attention to the surface instability, particularly surface reconstruction, including formation of NiO-type rock salt, [11,18,19] Li 2 CO 3 species, [10,14,[20][21][22] and nickel carbonate (NiCO 3 ·2Ni(OH) 2 ·2H 2 O). [23] These surface species are electrochemically inactive and poor in electronic and ionic conductivity, so causing high impedance to Li + (de)intercalation during cycling, [24,25] and even power fade as reported in LiNi 0.8 Co 0.2 O 2 . [26] The formation of NiO and Li 2 CO 3 at the surface of prima...

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Cathode‐Electrolyte‐Interphase Film Formation on a LiNiO₂ Surface in Conventional Aqueous Electrolytes: Simple Method to Improve the Electrochemical Performance of LiNiO₂ Electrodes for Use in Aqueous Li‐Ion Batteries

Lee

Yokoyama

Kondo

et al. 2021

Advanced Energy Materials

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Investigation and improvement on the electrochemical performance and storage characteristics of LiNiO2-based materials for lithium ion battery

Cited by 138 publications

References 34 publications

Chemical Weathering of Layered Ni-Rich Oxide Electrode Materials: Evidence for Cation Exchange

Chemical Weathering of Layered Ni-Rich Oxide Electrode Materials: Evidence for Cation Exchange

Cooling Induced Surface Reconstruction during Synthesis of High‐Ni Layered Oxides

Cathode‐Electrolyte‐Interphase Film Formation on a LiNiO₂ Surface in Conventional Aqueous Electrolytes: Simple Method to Improve the Electrochemical Performance of LiNiO₂ Electrodes for Use in Aqueous Li‐Ion Batteries

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Investigation and improvement on the electrochemical performance and storage characteristics of LiNiO2-based materials for lithium ion battery

Cited by 138 publications

References 34 publications

Chemical Weathering of Layered Ni-Rich Oxide Electrode Materials: Evidence for Cation Exchange

Chemical Weathering of Layered Ni-Rich Oxide Electrode Materials: Evidence for Cation Exchange

Cooling Induced Surface Reconstruction during Synthesis of High‐Ni Layered Oxides

Cathode‐Electrolyte‐Interphase Film Formation on a LiNiO2 Surface in Conventional Aqueous Electrolytes: Simple Method to Improve the Electrochemical Performance of LiNiO2 Electrodes for Use in Aqueous Li‐Ion Batteries

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Cathode‐Electrolyte‐Interphase Film Formation on a LiNiO₂ Surface in Conventional Aqueous Electrolytes: Simple Method to Improve the Electrochemical Performance of LiNiO₂ Electrodes for Use in Aqueous Li‐Ion Batteries