New Insight into High-Rate Performance Lithium-Rich Cathode Synthesis through Controlling the Reaction Pathways by Low-Temperature Intermediates

Qiu, Lang; Wang, Da-qiang; Chen, Ting; Li, Juan; Wu, Zhenguo; Song, Yang; Guo, Xiaodong

doi:10.1021/acs.iecr.1c04464

Cited by 7 publications

(6 citation statements)

References 54 publications

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“…Ni-rich materials were prepared by a high-temperature lithiation reaction. , The commercial precursor of Ni 0.86 Co 0.08 Mn 0.06 (OH) 2 was mixed with a slightly excessive quantity of LiOH·H 2 O (TM/Li = 1:1.02 molar ratio) by dry grinding. The sintering procedure is to place the mixture in an oxygen atmosphere and heat up to 480 °C with a heating rate of 5 °C min –1 and hold for 5 h and then increase to 750 °C at the same rate and hold for 20 h. The synthesized layered cathode material is named N86.…”

Section: Methodsmentioning

confidence: 99%

Understanding of the Irreversible Phase Transition and Zr-Doped Modification Strategy for a Nickel-Rich Cathode under a High Voltage

Chen

et al. 2022

ACS Sustainable Chem. Eng.

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Increasing the nickel content and broadening the voltage window are important means for LiNi x Co y Mn 1−x−y O 2 layered cathodes with low cost and high energy density, but these nickel-rich cathodes often suffer from structural instability and unsatisfactory cyclic performance. The systematic and detailed degradation mechanism especially under a high voltage is still unclear, which hinders the further development of nickel-rich cathodes. Our results show that due to the migration of high valence nickel ions to lithium sites, especially upon the deep removal of Li + ions, the nickel-rich cathode undergoes an irreversible phase transformation from a layered structure to a spinel or even rocksalt phase. Such irreversible phase transitions within a wide voltage window would cause insufficient lithium utilization and voltage decay, finally deteriorating the electrochemical performance of nickel-rich cathodes. In a narrow voltage range of 3.0−4.3 V, the capacity retention of the Ni-rich cathode is 93.4%, and the voltage fading is only 40 mV after 250 cycles. However, the cathode only exhibits a capacity retention of 77.4% with a significant voltage decay over 180 mV, as the voltage range further extends to 3.0−4.6 V. Furthermore, various characterizations and electrochemical performances demonstrate that the strengthened metal−oxygen bonds in the transition layer can produce stable structures and suppress phase transitions, thereby displaying superior electrochemical performance in the widened voltage window. As a result, the cycling retention of a Zr-doped cathode reaches 84.5%, and the voltage decay is only 50 mV after 250 cycles at 3.0−4.6 V, which exhibits excellent long-term cycle performance. These insights provide guidance for understanding the electrochemical mechanism and the design of high-voltage cathode materials.

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Section: Methodsmentioning

confidence: 99%

Understanding of the Irreversible Phase Transition and Zr-Doped Modification Strategy for a Nickel-Rich Cathode under a High Voltage

Chen

et al. 2022

ACS Sustainable Chem. Eng.

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“…For example, Li-rich cathode materials prepared by coprecipitation exhibit better electrochemical performances with Li2CO3 precursors (Y. Wang et al, 2023;C. Wu et al, 2022), while other cathode structures with different synthesis methods, including LMO via solid-state (P.-B.…”

Section: Research Articlementioning

confidence: 99%

Comparison of lithium sources on the electrochemical performance of LiNi0.5Mn1.5O4 cathode materials for lithium-ion batteries

Sudaryanto,

Salsabila,

Sari

et al. 2024

Int. J. Renew. Energy Dev.

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In order to fulfill the demand for high energy and capacity, an electrode with high-voltage capability, namely LiNi0.5Mn1.5O4 (LNMO) that has an operating potential of up to 4.7 V vs Li/Li+, is currently becoming popular in Li-ion battery chemistries. This research produced LNMO by using a solid-state method with only one-step synthesis route to compare its electrochemical performance with different lithium sources, including hydroxide (LNMO-LiOH), acetate (LNMO-LiAce), and carbonate (LNMO-LiCar) precursors. TGA/DSC was first performed for all three sample precursors to ensure the optimal calcination temperature, while XRD and SEM characterized the physical properties. The electrochemical measurements, including cyclic voltammetry and charge-discharge, were conducted in the half-cell configurations of LNMO//Li-metal using a standard 1 M LiPF6 electrolyte. LNMO-LiOH samples exhibited the highest purity and the smallest particle size, with values of 93.3% and 418 nm, respectively. In contrast, samples with higher impurities, such as LNMO-LiCar, mainly in the form of LixNi1-xO (LiNiO), displayed the largest particle size. The highest working voltage possessed by LNMO-LiOH samples was 4.735 V vs Li/Li+. The results showed that LNMO samples with LiNiO impurities would affect the reaction behavior that occurs at the cathode-electrolyte interface during the release of lithium-ions, resulting in high resistance at the battery operations and decreasing the specific capacity of the LNMO during discharging. The highest value, shown by LNMO-LiOH, was up to 92.75 mAh/g. On the other side, LNMO-LiCar only possessed a specific capacity of 44.57 mAh/g, indicating a significant impact of different lithium sources in the overall performances of LNMO cathode.

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“…The structural and compositional dependence of manganese-rich lithium insertion compounds on the lithium provided during synthesis was investigated . The selection of different lithium sources could control the reaction pathways of Ni 0.25 Mn 0.75 CO 3 in low temperature and then prepare the Li-rich cathode with high-rate performance . A lot of works show that the type of precursors and lithium source have an effect on the intermediate phase structure evolution, affecting the microstructure, particle size, and morphology of the final product, finally changing the electrochemical performance. − However, due to the complexity of the calcination process, there is still a lack of systematic research on the influence of the types of lithium sources on the evolution path selection of different precursors.…”

Section: Introductionmentioning

confidence: 99%

Evolution Path of Precursor-Induced High-Temperature Lithiation Reaction during the Synthesis of Lithium-Rich Cathode Materials

Wu,

Ban,

Chen

et al. 2024

ACS Omega

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High-temperature lithiation is one of the crucial steps for the synthesis of Li-and Mn-rich layered metal oxide (LMLO) cathodes. A profound insight of the micromorphology and crystal structure evolution during calcination helps to realize the finely controlled preparation of final cathodes, finally achieving a desired electrochemical performance. In this work, two typical precursors (hydroxide and oxalate) were selected to prepare LMLO. It is found that the influence of the lithium source on reaction pathways is determined by the properties of precursors. In the case of hydroxide as a precursor, whatever lithium sources it is, the flake morphology of LMLO is inherited from hydroxide precursors. This is because the crystal structure of cathode products has a high similarity with its precursor in terms of the oxygen array arrangement, and the topological transformation occurs from hydroxide (P-3ml) to LMLOs (C/2m and R3m). Thus, the morphology and microstructure of LMLO cathodes could be well controlled only by tuning the properties of hydroxide precursors. Conversely, the decomposition of a lithium source has a great influence on the intermediate transformation when oxalate is used as the precursor. This is because a large amount of CO 2 is released from the oxalate precursor after the decomposition reaction, resulting in drastic structural changes. At this time, the diffusion ability of the lithium source leads to the competition between the spinel phase and layered phase. Based on this point, the formation of a spinel intermediate phase can be reduced by accelerating the decomposition of the lithium source, contributing to the generation of a highly pure layered phase, thus exhibiting higher electrochemical performance. These insights provide an exciting cue to the rational selection and design of raw materials and lithium sources for the controlled synthesis of LMLO cathodes.

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New Insight into High-Rate Performance Lithium-Rich Cathode Synthesis through Controlling the Reaction Pathways by Low-Temperature Intermediates

Cited by 7 publications

References 54 publications

Understanding of the Irreversible Phase Transition and Zr-Doped Modification Strategy for a Nickel-Rich Cathode under a High Voltage

Understanding of the Irreversible Phase Transition and Zr-Doped Modification Strategy for a Nickel-Rich Cathode under a High Voltage

Comparison of lithium sources on the electrochemical performance of LiNi0.5Mn1.5O4 cathode materials for lithium-ion batteries

Evolution Path of Precursor-Induced High-Temperature Lithiation Reaction during the Synthesis of Lithium-Rich Cathode Materials

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