Li1.3Al0.3Ti1.7(PO4)3包覆LiNi0.8Co0.1Mn0.1O2正极材料的电化学性能研究

doi:10.16553/j.cnki.issn1000-985x.2025.0126

摘要/Abstract

摘要： 本文采用共沉淀法制备Ni_0.8Co_0.1Mn_0.1O₂（OH）₂前驱体，通过煅烧制备了LiNi_0.8Co_0.1Mn_0.1O₂（NCM811）正极材料，分别采用1%、2%和3%（质量分数，下同）的Li_1.3Al_0.3Ti_1.7（PO₄）₃（LATP）对NCM811进行包覆改性研究。结果表明：当LATP包覆量为2%时，在3.0~4.3 V条件下循环350次后，容量的保持率为84.65%，而未包覆的NCM811在同样条件下的容量保持率为80.58%。倍率性能测试结果表明，在10 C时，2%LATP样品的放电比容量为117.1 mAh·g^-1，未包覆的NCM811样品为101.8 mAh·g^-1。适量的LATP包覆可提高锂离子扩散速率，优化离子传输路径，同时，LATP作为包覆层可以避免正极材料与电解液的直接接触，减少副反应的发生，从而降低界面阻抗，提高循环寿命。

关键词: LATP; LiNi_0.8Co_0.1Mn_0.1O₂; 表面包覆; 三元正极材料; 高镍; 包覆改性

Abstract: The precursor Ni_0.8Co_0.1Mn_0.1O₂（OH）₂ was generated by co-precipitation， and LiNi_0.8Co_0.1Mn_0.1O₂（NCM811）， the cathode material， was prepared by calcination. The coating modification of NCM811 was investigated utilizing various amounts of Li_1.3Al_0.3Ti_1.7（PO₄）₃ （LATP） coating （mass fraction of 1%， 2%， and 3%）. The results show that the capacity retention rate is 84.65% after 350 cycles at 3.0~4.3V， while the capacity retention rate of the uncoated NCM811 is 80.58% when the LATP coating amount is 2%. The rate performance test indicates that the discharge specific capacity of the LATP （2%） sample is 117.1 mAh·g^-1 at 10 C， while the uncoated NCM811 sample has a specific capacity of 101.8 mAh·g^-1. Therefore， we can conclude that an appropriate amount of LATP coating can enhance the lithium ions diffusion rate and optimize the ion transport pathways. Simultaneously， as a coating layer， LATP prevents direct contact between the cathode material and the electrolyte， reducing side reactions. This， in turn， lowers the interfacial impedance and improves the cycling life.

Key words: LATP; LiNi_0.8Co_0.1Mn_0.1O₂; surface coating; ternary cathode material; Ni-rich; coating modification

中图分类号:

TM912

姚年春, 何玉林, 张闽, 王自强. Li_1.3Al_0.3Ti_1.7(PO₄)₃包覆LiNi_0.8Co_0.1Mn_0.1O₂正极材料的电化学性能研究[J]. 人工晶体学报, 2025, 54(12): 2209-2216.

YAO Nianchun, HE Yulin, ZHANG Min, WANG Ziqiang. Electrochemical Performance of LiNi_0.8Co_0.1Mn_0.1O₂ Cathode Material with Li_1.3Al_0.3Ti_1.7(PO₄)₃ Coating[J]. Journal of Synthetic Crystals, 2025, 54(12): 2209-2216.

图/表 11

图1 LATP包覆NCM811原理示意图

Fig.1 Schematic diagram of LATP-coated on NCM811

图2 NCM811和包覆LATP（1%、2%和3%）样品的XRD图谱

Fig.2 XRD patterns of NCM811 and LATP-coated （1%， 2% and 3%） samples

表1 NCM811和包覆LATP的NCM811的晶格参数

Table 1 Lattice parameters of the pristine NCM811 and LATP-coated NCM811

Sample	a/Å	c/Å	c/a	I_（003）/I_（104）
NCM811	2.868 0	14.269 1	4.975	1.329
LATP1	2.868 2	14.271 1	4.976	1.332
LATP2	2.869 0	14.269 3	4.974	1.371
LATP3	2.869 0	14.265 0	4.972	1.357

图3 NCM811（a）、LATP1（b）、LATP 2（c）、LATP3（d）的SEM照片和LATP2的EDS图谱（e）~（f）

Fig.3 SEM images of NCM811 （a）， LATP1 （b）， LATP2 （c）， LATP3 （d） and EDS mapping of LATP2 （e）~（f）

图4 NCM811（a）、（b）和LATP2样品（c）、（d）的TEM和HRTEM照片

Fig.4 TEM and HRTEM images of bare NCM811 （a），（b） and LATP2 （c），（d）

图5 不同样品的首次充放电容量曲线图

Fig.5 Initial charge-discharge curves of different samples

图6 不同样品在25 ℃下的循环性能

Fig.6 Cycling performances of different samples at 25 ℃

表2 不同样品在0.1 C下的首次充放电容量及库仑效率

Table 2 Initial charge-discharge capacity and columbic efficiency of different samples at 0.1 C

Sample	Charge capacity/（mAh·g^-1）	Discharge capacity/（mAh·g^-1）	Irreversible capacity/（mAh·g^-1）	Coulombic efficiency/%
NCM811	218.9	176.4	42.5	80.58
LATP1	223.4	181.1	42.3	81.06
LATP2	227.5	192.6	34.9	84.65
LATP3	223.8	184.9	38.9	82.62

图7 不同样品的倍率曲线

Fig.7 Rate capabilities of different samples

图8 NCM811和LATP2的EIS结果。（a）循环5次；（b）循环350 次

Fig.8 EIS results of pristine NCM811 and LATP2 sample. （a） After 5 cycles；（b） after 350 cycles

表3 NCM811和LATP2的动力学参数

Table 3 Kinetic parameters of NCM811 and LATP2

Sample	NCM811			LATP2
Sample	R_s/Ω	R_f/Ω	R_ct/Ω	R_s/Ω	R_f/Ω	R_ct/Ω
After 5 cycles	5.757	10.17	15.91	6.662	17.42	31.41
After 350 cycles	9.562	12.09	63.33	3.864	18.41	25.21

参考文献 24

[1]	CROY J R， KIM D， BALASUBRAMANIAN M， et al. Countering the voltage decay in high capacity xLi₂MnO₃·（1-x）LiMO₂Electrodes （M=Mn， Ni， Co） for Li⁺-ion batteries［J］. Journal of the Electrochemical Society， 2012， 159（6）： A781-A790.
[2]	LIU Y J， WANG Q L， ZHANG Z Q， et al. Investigation the electrochemical performance of layered cathode material Li_1.2Ni_0.2Mn_0.6O₂ coated with Li₄Ti₅O₁₂ ［J］. Advanced Powder Technology， 2016， 27（4）： 1481-1487.
[3]	JOHNSON C S， LI N C， LEFIEF C， et al. Synthesis， characterization and electrochemistry of lithium battery electrodes： xLi₂MnO₃·（1-x）LiMn_0.333Ni_0.333Co_0.333O₂ （0≤x≤0.7）［J］. Chemistry of Materials， 2008， 20（19）： 6095-6106.
[4]	YIN S Y， CHEN H Y， CHEN J， et al. Chemical-mechanical effects in Ni-rich cathode materials［J］. Chemistry of Materials， 2022， 34（4）： 1509-1523.
[5]	宁静蓉. 高电压锂离子电池电解液在电极界面作用的机制研究［D］. 武汉：湖北大学， 2022.
	NING J R. Study on the mechanism of electrolyte interaction at electrode interface in high voltage lithium ion battery［D］. Wuhan： Hubei University， 2022 （in Chinese）.
[6]	XU X， ZHU H， TANG Y， et al. Spreading monoclinic boundary network between hexagonal primary grains for high performance Ni-rich cathode materials［J］. Nano Energy， 2022， 100： 107502.
[7]	ANH V T， TRAN VU H A， NGUYEN V H， et al. Enhancing electrochemical performance of Ni-rich cathodes for Li-ion batteries through spatial atomic layer deposition of ZnO coatings［J］. Materials Chemistry and Physics， 2025， 336： 130544.
[8]	FENG Y H， XU H， WANG B， et al. Enhanced electrochemical performance of LiNi_0.8Co_0.1Mn_0.1O₂ cathode materials by Al₂O₃ coating［J］. Journal of Electrochemical Energy Conversion and Storage， 2021， 18（3）： 031005.
[9]	SHIM J H， LEE S H， PARK S S. Effects of MgO coating on the structural and electrochemical characteristics of LiCoO₂ as cathode materials for lithium ion battery［J］. Chemistry of Materials， 2014， 26（8）： 2537-2543.
[10]	PENG Z D， HUANG M， WANG W G， et al. Enhancing the structure and interface stability of LiNi_0.83Co_0.12Mn_0.05O₂ cathode material for Li-ion batteries via facile CeP₂O₇ coating［J］. ACS Sustainable Chemistry & Engineering， 2022， 10（15）： 4881-4893.
[11]	VÁSQUEZ F A， ROSERO-NAVARRO N C， MIURA A， et al. Beneficial effect of LiFePO₄/C coating on Li_0.9Mn_1.6Ni_0.4O₄ obtained by microwave heating［J］. Electrochimica Acta， 2023， 437： 141544.
[12]	LIU W， OH P， LIU X E， et al. Countering voltage decay and capacity fading of lithium-rich cathode material at 60 ℃ by hybrid surface protection layers［J］. Advanced Energy Materials， 2015， 5（13）： 1500274.
[13]	HU G R， ZHANG M F， WU L L， et al. Effects of Li₂SiO₃ coating on the performance of LiNi_0.5Co_0.2Mn_0.3O₂ cathode material for lithium ion batteries［J］. Journal of Alloys and Compounds， 2017， 690： 589-597.
[14]	ZHAN X W， GAO S， CHENG Y T. Influence of annealing atmosphere on Li₂ZrO₃-coated LiNi_0.6Co_0.2Mn_0.2O₂ and its high-voltage cycling performance［J］. Electrochimica Acta， 2019， 300： 36-44.
[15]	LIU Y J， FAN X J， HUANG X， et al. Electrochemical performance of Li_1.2Ni_0.2Mn_0.6O₂ coated with a facilely synthesized Li_1.3Al_0.3Ti_1.7（PO₄）₃ ［J］. Journal of Power Sources， 2018， 403： 27-37.
[16]	陈家有. 氮化碳均匀包覆Li_1.3Al_0.3Ti_1.7（PO₄）₃在复合固态电解质膜中的应用及机理研究［D］. 青岛：青岛大学， 2024.
	CHEN J Y. Application and mechanism study of carbon nitride uniformly coated Li_1.3Al_0.3Ti_1.7（PO₄）₃ in composite solid state electrolyte membrane［D］. Qingdao： Qingdao University， 2024 （in Chinese）.
[17]	李潇逸. 固态锂电池的Li_1.3Al_0.3Ti_1.7（PO₄）₃固体电解质制备及界面修饰［D］. 徐州：中国矿业大学， 2023.
	LI X Y. Preparation and Interfacial Modification of Li_1.3Al_0.3Ti_1.7（PO₄）₃ solid electrolytes for solid state lithium battery［D］. Xuzhou： China University of Mining and Technology， 2023 （in Chinese）.
[18]	刘圣奇，杨晨，张真硕，等. 原位构建ZnO梯度缓冲层对Li\|LATP界面稳定性的研究［J］. 材料科学， 2025， 15（4）： 816-824.
	LIU S Q， YANG C， ZHANG Z S， et al. Study on the stability of Li\|LATP interface by in-situ ZnO gradient buffer layer［J］. Material Sciences， 2025， 15（4）： 816-824 （in Chinese）.
[19]	TSAI D L， YEH C N. Modifying Li_1.3Al_0.3Ti_1.7（PO₄）₃electrolyte-anode interface with two-dimensional materials for all-solid-state lithium batteries［J］. ECS Meeting Abstracts， 2024， MA2024-02（8）： 1134.
[20]	JEONG W， LIU L Y， LIM H S， et al. A study on the improvement of ion conductivity of lithium aluminum titanium phosphate-based solid-state electrolyte by the addition of divalent cations［J］. Journal of the Korean Ceramic Society， 2025， 62（1）： 83-89.
[21]	HE Y L， LI Y， YAO N C， et al. Modification of LiNi_0.5Co_0.2Mn_0.3O₂ with a NaAlO₂ coating produces a cathode with increased long-term cycling performance at a high voltage cutoff［J］. Ceramics International， 2020， 46（6）： 7625-7633.
[22]	YU H F， WANG S L， HU Y J， et al. Lithium-conductive LiNbO₃ coated high-voltage LiNi_0.5Co_0.2Mn_0.3O₂ cathode with enhanced rate and cyclability［J］. Green Energy & Environment， 2022， 7（2）： 266-274.
[23]	ZENG X F， JIAN T Z， LU Y， et al. Enhancing high-temperature and high-voltage performances of single-crystal LiNi_0.5Co_0.2Mn_0.3O₂ cathodes through a LiBO₂/LiAlO₂ dual-modification strategy［J］. ACS Sustainable Chemistry & Engineering， 2020， 8（16）： 6293-6304.
[24]	WANG L， HU Y H. Surface modification of LiNi_0.5Co_0.2Mn_0.3O₂ cathode materials with Li₂O-B₂O₃-LiBr for lithium-ion batteries［J］. International Journal of Energy Research， 2019， 43（9）： 4644-4651.

Li_1.3Al_0.3Ti_1.7(PO₄)₃包覆LiNi_0.8Co_0.1Mn_0.1O₂正极材料的电化学性能研究

Electrochemical Performance of LiNi_0.8Co_0.1Mn_0.1O₂ Cathode Material with Li_1.3Al_0.3Ti_1.7(PO₄)₃ Coating

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 11

参考文献 24

相关文章 5

编辑推荐

Metrics

本文评价

[1]	刘琳琳, 刘杰, 陈前林, 罗诗键, 李翠芹. LiZr₂(PO₄)₃包覆对高镍三元正极材料结构及电化学性能的影响[J]. 人工晶体学报, 2022, 51(4): 695-703.
[2]	王皓逸, 邹昱凌, 孟奇, 夏广辉, 林艳, 张英杰. 退役三元锂离子电池正极材料高效清洁回收技术研究进展[J]. 人工晶体学报, 2021, 50(6): 1158-1169.
[3]	谭燚;缪畅;聂炎;肖围. 废旧锂离子电池三元正极材料的回收与再利用工艺研究进展[J]. 人工晶体学报, 2020, 49(10): 1944-1951.
[4]	何海亮;吴显明;陈上;丁其晨;陈守彬. 锂离子固体电解质Li1.3Al0.3Ti1.7(PO4)3的合成与表征[J]. 人工晶体学报, 2015, 44(1): 195-199.
[5]	徐金琴;张霞;王路明. Li+掺杂ZnO基荧光粉的制备、性能研究及其表面包覆[J]. 人工晶体学报, 2012, 41(1): 227-231.