Utilizing fast ion conductor for single-crystal Ni-rich cathodes to achieve dual-functional modification of conductor network constructing and near-surface doping

Zhou, Xin’an; Zhang, Feilong; Fu, Xinghu; Zhang, Ningshuang; Huang, Jin; Cai, Xingpeng; Ding, Hao; Li, Baoqiang; Niu, Lei; Li, Shiyou

doi:10.1016/j.ensm.2022.07.029

Cited by 43 publications

(14 citation statements)

References 48 publications

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“…The overgrown CEI layer with large amount of LiF leads to increase of cell impedance, thereby hindering the Li + transport and reducing the electrochemical activity of the material. [ 17 ] The increased impedance is supported by the EIS results shown in Figure S20 and Table S7 (Supporting Information).…”

Section: Resultsmentioning

confidence: 71%

Tungsten Boride Stabilized Single‐Crystal LiNi_0.83Co_0.07Mn_0.1O₂ Cathode for High Energy Density Lithium‐Ion Batteries: Performance and Mechanisms

Zhang

Deng

Zhong

et al. 2023

Adv Funct Materials

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Transition metal doped LiNiO2 layered compounds have attracted significant interest as cathode materials for lithium‐ion batteries (LIBs) in recent years due to their high energy density. However, a critical issue of LiNiO2‐based cathodes is caused particularly at highly delithiated state by irreversible phase transition, initiation/propagation of cracks, and extensive reactions with electrolyte. Herein, a tungsten boride (WB)‐doped single‐crystalline LiNi0.83Co0.07Mn0.1O2 (SNCM) cathode is reported that affectively addresses these drawbacks. In situ/ex situ microscopic and spectroscopic evidence that B3+ enters the bulk of the SNCM, enlarging the interlayer spacing, thus facilitating Li+ diffusion, while W3+ forms an amorphous surface layer consisting of LixWyOz (LWO) and LixByOz (LBO), which aids the construction of a robust cathode‐electrolyte interphase (CEI) film, are shown. It is also shown that WB doping is effective in controlling the degree of the c‐axis contraction and release of oxygen‐containing gases at high voltages. The best doping concentration of WB is 0.6 wt.%, at which the capacity retention rate of the SNCM reaches 93.2% after 200 cycles at 2.7–4.3 V, while the morphology and structure of the material remain largely unchanged. The presented modification strategy offers a new way for the design of new stable SNCM cathodes for high‐energy‐density LIBs.

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Section: Resultsmentioning

confidence: 71%

Tungsten Boride Stabilized Single‐Crystal LiNi_0.83Co_0.07Mn_0.1O₂ Cathode for High Energy Density Lithium‐Ion Batteries: Performance and Mechanisms

Zhang

Deng

Zhong

et al. 2023

Adv Funct Materials

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“…With the successful commercialization and wide application of the nickel-rich layered oxide-based lithium ion batteries for electric vehicles (EVs), minimizing the cobalt content in the materials has received increasing attention due to the limited cobalt supplies. − Nickel-rich materials, stemming from LiNiO 2 partially substituted with elements other than nickel to stabilize the structure of LiNiO 2 , can provide a relatively high capacity (>200 mAh g –1 ) and voltage platform (∼3.6 V), which are crucial to the lithium ion batteries with high energy density to meet the driving range requirement of EVs. However, the presence of cobalt in the materials seems to be essential to gain the superior performance of the materials, such as in the cases of the commercialized LiNi 1– x – y Co x Al y O 2 (NCA) − and LiNi 1– x – y Co x Mn y O 2 (NCM). − It has been suggested that the presence of Co would lead to a well-crystallized layered structure compared to the pristine counterpart LiNiO 2 . In addition, the orbital overlap between the Co 3+/4+ :3d band and the O 2– :2p band would reduce the impedance for the charge transfer and benefit the rate capability of the electrodes .…”

Section: Introductionmentioning

confidence: 99%

Simultaneous Bulk Doping and Surface Coating of Sn to Boost the Electrochemical Performance of LiNiO₂

Wen

Zhou

et al. 2023

ACS Appl. Energy Mater.

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Co-free, nickel-rich layered materials are crucial for the cost reduction of lithium ion batteries to meet the requirement of the electric vehicle market. However, the strategies to synthesize the practically applicable Co-free, nickel-rich materials are still challenging. Herein, we report a strategy for fabrication of the materials by Sn modification of LiNiO 2 . Under high temperature conditions, bulk doping of the Sn 4+ ions and surface coating of Li 2 SnO 3 can be simultaneously achieved. Due to the presence of the strong Sn−O bond and chemically inert property of the coating layer, the structure reversibility, integrity of the secondary particles, and interfacial stability of the Sn-modified materials during charge/discharge cycling can be greatly enhanced relative to those of the counterpart pristine LiNiO 2 . The optimized material, LiNi 0.97 Sn 0.03 O 2 , can deliver a discharge capacity of 216.76 mAh g −1 at 0.1 C with a capacity retention of 80.61% after 250 cycles at 0.5 C. In addition, the enlargement of the crystal lattice by Sn doping is also beneficial to the rate capability of the materials, providing a discharge capacity of 148.06 mAh g −1 at 5 C. Thus, the simultaneous dual functionalization of Sn to LiNiO 2 could be a practicable approach to gaining the Co-free, nickel-rich materials.

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“…Based on the complementary advantages of bulk doping and surface modification, some dual-modification strategy were proposed. It has been reported that Mg 2+ doping and surface poly pyrrole (PPy) coating, Ti 4+ doping and TiNb 2 O 7 coating, Nb 5+ near-surface doping and Li 5 La 3 Nb 2 O 12 coating, Zr 4+ doping and LiBO 3 /B 2 O 3 coating, and Zr 4+ doping and La 2 Zr 2 O 7 nanoshell − all play a synergistic role in improving both the structural and interfacial stability. Unfortunately, the present dual-modification strategies have the common problem of complicated multistep reaction routes in the experimental synthesis process .…”

Section: Introductionmentioning

confidence: 99%

Simple Synchronous Dual-Modification Strategy with Zr⁴⁺ Doping and CeO₂ Nanowelding to Stabilize Layered Ni-Rich Cathode Materials

Liu

Yin

Zheng

et al. 2023

ACS Appl. Energy Mater.

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A Ni-rich layered oxide, one promising cathode for lithium-ion batteries (LIBs), exhibits the advantages of low cost and high capacity but suffers from rapid capacity loss due to bulk structural instability and surface side reactions. Herein, a simple synchronous dual-modification strategy with Zr4+ doping and CeO2 nanowelding is proposed to address such issues. Utilizing the migration energy difference of Zr and Ce ions in layered structures, one-step high-temperature sintering of LiNi0.8Co0.1Mn0.1O2 particles with Zr and Ce nitrate distributions enables simultaneous doping of Zr ions in the bulk and CeO2 surface modification. Therein, Zr ions in the bulk occupying the Li sites can improve the Li+ diffusion rate and stabilize the crystal structure, while CeO2 on the surface provides nanowelding between the grain boundaries and resistance to electrolyte erosion. Theoretical calculations and a series of structure/composition characterizations (i.e., neutron scattering, in situ X-ray diffraction, etc.) validated the proposed strategy and its role in stabilizing the Ni-rich cathodes. The synergistic effect of Zr4+ doping and CeO2 nanowelding enables an impressive initial capacity of 187.2 mAh g–1 (2.7–4.3 V vs Li/Li+) with 86.1% retention after 200 cycles at 1 C and rate capabilities of 146.6 and 127.3 mAh g–1 at 5 and 10 C, respectively. Upon increasing the testing temperature to 60 °C, the dual-modified Ni-rich cathode exhibits an initial discharge capacity of 203.5 mAh g–1 with a good retention of 80.8% after 100 cycles at 0.5 C. The present strategy utilizing the migration energy difference of metal ions to achieve synchronous bulk doping and surface modification will offer fresh insights to stabilize layered cathode materials for LIBs, which can be widely used in other kinds of batteries with various cathode materials.

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Utilizing fast ion conductor for single-crystal Ni-rich cathodes to achieve dual-functional modification of conductor network constructing and near-surface doping

Cited by 43 publications

References 48 publications

Tungsten Boride Stabilized Single‐Crystal LiNi_0.83Co_0.07Mn_0.1O₂ Cathode for High Energy Density Lithium‐Ion Batteries: Performance and Mechanisms

Tungsten Boride Stabilized Single‐Crystal LiNi_0.83Co_0.07Mn_0.1O₂ Cathode for High Energy Density Lithium‐Ion Batteries: Performance and Mechanisms

Simultaneous Bulk Doping and Surface Coating of Sn to Boost the Electrochemical Performance of LiNiO₂

Simple Synchronous Dual-Modification Strategy with Zr⁴⁺ Doping and CeO₂ Nanowelding to Stabilize Layered Ni-Rich Cathode Materials

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Utilizing fast ion conductor for single-crystal Ni-rich cathodes to achieve dual-functional modification of conductor network constructing and near-surface doping

Cited by 43 publications

References 48 publications

Tungsten Boride Stabilized Single‐Crystal LiNi0.83Co0.07Mn0.1O2 Cathode for High Energy Density Lithium‐Ion Batteries: Performance and Mechanisms

Tungsten Boride Stabilized Single‐Crystal LiNi0.83Co0.07Mn0.1O2 Cathode for High Energy Density Lithium‐Ion Batteries: Performance and Mechanisms

Simultaneous Bulk Doping and Surface Coating of Sn to Boost the Electrochemical Performance of LiNiO2

Simple Synchronous Dual-Modification Strategy with Zr4+ Doping and CeO2 Nanowelding to Stabilize Layered Ni-Rich Cathode Materials

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Tungsten Boride Stabilized Single‐Crystal LiNi_0.83Co_0.07Mn_0.1O₂ Cathode for High Energy Density Lithium‐Ion Batteries: Performance and Mechanisms

Tungsten Boride Stabilized Single‐Crystal LiNi_0.83Co_0.07Mn_0.1O₂ Cathode for High Energy Density Lithium‐Ion Batteries: Performance and Mechanisms

Simultaneous Bulk Doping and Surface Coating of Sn to Boost the Electrochemical Performance of LiNiO₂

Simple Synchronous Dual-Modification Strategy with Zr⁴⁺ Doping and CeO₂ Nanowelding to Stabilize Layered Ni-Rich Cathode Materials