电/离子导体双包覆的LiNi0.8Co0.1Mn0.1O2锂离子电池阴极材料及其电化学性能

doi:10.6023/A21120600

摘要/Abstract

高镍三元材料LiNi_0.8Co_0.1Mn_0.1O₂ (NCM)比容量高且成本低, 但材料结构在电化学循环过程中的不稳定性影响了其大规模的应用, 可采用表面包覆的策略来改善材料的结构稳定性, 从而提高其电化学性能. 本工作结合高速固相包覆法和高温烧结法, 分别将电子导体氧化锡锑(ATO)和锂离子导体偏磷酸锂(LOP)共同包覆在NCM材料表面. 双包覆后的NCM材料的电子电导率从2.17×10^-3 Ѕ•cm^-1提高至1.02×10^-2 Ѕ•cm^-1, 锂离子扩散系数也从7.05×10^-9 cm²•s^-1提高至2.88×10^-8 cm²•s^-1. 同时, NCM表面的双包覆层可以在循环过程中阻止电极材料与电解液发生氧化还原反应, 抑制材料不利相变, 减少氧的析出, 稳定材料结构. 电化学性能测试表明, 经过表面包覆后, NCM材料在1 C (180 mA•g^-1)的电流下和2.7~4.3 V (vs. Li/Li⁺)的电压范围内, 循环150周后容量为161.1 mAh•g^-1, 保持率为87.1%, 而在10 C的充放电倍率下具有133 mAh•g^-1的可逆比容量.

关键词: 锂离子电池, 富镍阴极材料, 电子导体, 锂离子导体, 快速充电

The Ni-rich layered cathode material LiNi_0.8Co_0.1Mn_0.1O₂ presents a high specific capacity and relatively low cost, however, the inherent structure instability during the electrochemical cycling process hinders its application widely. Universally, the strategy of surface coating can be used to improve the structural stability of the material and then improve its electrochemical performance. This work combines the high-speed solid-phase coating method and the high-temperature sintering method to coat the electronic conductor antimony tin oxide and lithium-ion conductor lithium metaphosphate on the surface of the LiNi_0.8Co_0.1Mn_0.1O₂ material, respectively. The electron/ion conductor double coating layer forms a charge conversion and transport channel on the surface of the LiNi_0.8Co_0.1Mn_0.1O₂. The electronic conductivity of the double-coated LiNi_0.8Co_0.1Mn_0.1O₂ material increased from 2.17×10^-3 Ѕ•cm^-1 to 1.02×10^-2 Ѕ•cm^-1, and the diffusion coefficient of lithium-ion also increased from 7.05×10^-9 cm²•s^-1 to 2.88×10^-8 cm²•s^-1. At the same time, due to strong P—O bonds and stable metal oxides, the double-coating layer on the surface of the LiNi_0.8Co_0.1Mn_0.1O₂ material can effectively restrain the irreversible phase transitions, and it also can inhibit the interfacial reactions under high electrode potential. The electrochemical performance test demonstrated that the cyclability and rate performance of LiNi_0.8Co_0.1Mn_0.1O₂ material improved due to surface modification. The cathode assembled with double-coated LiNi_0.8Co_0.1Mn_0.1O₂ material can maintain a reversible capacity of 161.1 mAh•g^-1 after 150 cycles at 1 C (after being activated at 0.1 C for two cycles, 1 C=180 mA•g^-1) during 2.7~4.3 V (vs. Li/Li⁺), with a capacity retention of 87.1%. This coated LiNi_0.8Co_0.1Mn_0.1O₂ material also displays a specific capacity as high as 133 mAh•g^-1 at 10 C. In comparison, the pristine LiNi_0.8Co_0.1Mn_0.1O₂ delivers a capacity of only 113 mAh•g^-1 after 100 cycles and a reversible capacity retention rate of less than 60% (a decay rate of 0.4% per cycle).

Key words: lithium-ion battery, nickel-rich cathode material, electronic conductor, lithium-ion conductor, fast charging

引用此文

陈守潇, 刘君珂, 郑伟琛, 魏国祯, 周尧, 李君涛. 电/离子导体双包覆的LiNi_0.8Co_0.1Mn_0.1O₂锂离子电池阴极材料及其电化学性能[J]. 化学学报, 2022, 80(4): 485-493.

Shouxiao Chen, Junke Liu, Weichen Zheng, Guozhen Wei, Yao Zhou, Juntao Li. Electron/ion Conductor Double-coated LiNi_0.8Co_0.1Mn_0.1O₂ Li-ion Battery Cathode Material and Its Electrochemical Performance[J]. Acta Chimica Sinica, 2022, 80(4): 485-493.

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图/表 7

图1. NCM (a)和ATO@NCM (b)的SEM图. (c) ATO-LOP@NCM-2的SEM图和EDS图. (d) ATO-LOP@NCM-2的XPS全谱图. (e) ATO-LOP@NCM-x (x=1, 2和3)和NCM四种材料的XRD衍射图谱

Figure 1. The SEM images of pristine NCM (a) and ATO@NCM (b). (c) SEM images and EDS images of ATO-LOP@NCM-2. (d) The XPS full spectra of ATO-LOP@NCM-2. (e) The XRD diffraction patterns of ATO-LOP@NCM-x (x=1, 2 and 3) and Pristine NCM

图2. (a~c) ATO-LOP@NCM-2低倍率和高分辨下的TEM图. (d~e) 通过电子能量损失谱得出的ATO-LOP@NCM-2的元素分布

Figure 2. (a~c) TEM images of ATO-LOP@NCM-2 material at low magnification and high resolution. (d~e) The element distribution of ATO-LOP@NCM-2 obtained from the electron energy loss spectrum mapping

图3. (a) ATO-LOP@NCM-x (x=1, 2和3)和NCM四种材料的循环性能测试图. (b) ATO-LOP@NCM-x (x=1, 2和3)和NCM四种材料的倍率性能测试图. (c~f) ATO-LOP@NCM-x (x=1, 2和3)和NCM四种材料分别在循环1周、50周、100周后的充放电曲线

Figure 3. (a) Long-cycle performance of ATO-LOP@NCM-x (x=1, 2 and 3) and Pristine NCM. (b) Rate performance of ATO-LOP@NCM-x (x=1, 2 and 3) and Pristine NCM. (c~f) Charge and discharge curves of ATO-LOP@NCM-x (x=1, 2 and 3) and Pristine NCM after 1st, 50th, and 100th cycles respectively

图4. (a) NCM、ATO@NCM和ATO-LOP@NCM-2三种电极材料的电子电导率. (b, c) ATO-LOP@NCM-2和NCM的循环伏安曲线. (d) ATO-LOP@NCM-2和NCM的IP-v1/2曲线. (e) 通过IP-v1/2曲线计算出来的锂离子扩散系数(DLi+). (f, g) ATO-LOP@NCM-x (x=1, 2和3)和NCM四种材料循环前(f)和循环100周(g)后的电化学阻抗谱(EIS). (h)通过拟合电路得出的电阻数据

Figure 4. (a) The electronic conductivity of NCM, ATO@NCM, and ATO-LOP@NCM-2. (b, c) Cyclic voltammetry curves of ATO-LOP@NCM-2 and Pristine NCM. (d) The IP-v1/2 curves of ATO-LOP@NCM-2 and Pristine NCM. (e) Diffusion coefficient of lithium-ion (DLi+) calculated from the IP-v1/2 curves. (f, g) electrochemical impedance spectroscopy (EIS) of ATO-LOP@NCM-x (x=1, 2 and 3) and Pristine NCM before cycle (f) and after 100 cycles (g). (h) Resistance data obtained by fitting the equivalent circuit model

图5. NCM (a)和ATO-LOP@NCM-2 (b)在循环1周、50周和100周后的dQ/dV曲线. NCM (c)和ATO-LOP@NCM-2 (d)在17.2°~20.0°范围内充放电循环两周的原位XRD (2.7~4.3 V, 0.3 C)等高线图

Figure 5. dQ/dV curves during 1st, 50th, and 100th charging and discharging process of pristine NCM (a) and ATO-LOP@NCM-2 (b). In situ XRD contour maps (2.7~4.3 V, 0.3 C) over the range of 17.2°~20.0° of Pristine NCM (c) and ATO-LOP@NCM-2 (d) during 2 cycles

图6. NCM和ATO-LOP@NCM-2材料经过100周循环后的截面SEM图

Figure 6. SEM images of the cross-section of Pristine NCM and ATO-LOP@NCM-2 after 100 cycles

图7. 原始NCM电极在100次循环后的(a) C 1s、(b) O 1s 和(c) F 1s以及ATO-LCO@NCM-2电极在100次循环后的(d) C 1s、(e) O 1s和(f) F 1s的XPS谱

Figure 7. XPS spectra of (a) C 1s, (b) O 1s and (c) F 1s for pristine NCM electrode after 100 cycles and (d) C 1s, (e) O 1s and (f) F 1s for the ATO-LCO@NCM-2 electrode after 100 cycles

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电/离子导体双包覆的LiNi_0.8Co_0.1Mn_0.1O₂锂离子电池阴极材料及其电化学性能

Electron/ion Conductor Double-coated LiNi_0.8Co_0.1Mn_0.1O₂ Li-ion Battery Cathode Material and Its Electrochemical Performance

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