Li+掺杂诱导缺陷工程增强钙钛矿型高熵氧化物储锂性能

doi:10.11949/0438-1157.20251156

摘要/Abstract

摘要：

为解决高熵氧化物（HEOs）在储能领域面临的本征电导率低、锂离子传输动力学缓慢等问题，本研究采用溶液燃烧法制备了不同 Li⁺掺杂量的钙钛矿型La （CoCrFeMnNiLix）₁/（_5+x） O₃（x=0、0.2、0.4、0.6）HEOs负极材料，通过调控晶格畸变与氧空位等本征缺陷，实现储锂性能的显著提升。电化学测试表明，Li⁺掺杂可有效优化材料的电化学性能，其中Li0.4电极展示了卓越的倍率性能和循环稳定性，在 200 mA g^-1电流密度下循环 150 圈后放电比容量达 549.1 mAh g^-1，较未掺杂提升55.3%；1000 mA g^-1 下循环 500 圈，仍保持 503.6 mAh g^-1的可逆比容量（未掺杂样品为440 mAh g^-1）。其优异性能可归因于晶格畸变与高浓度氧空位的耦合调控作用，一方面优化电子/离子传输路径，增加反应活性位点；另一方面显著提升锂离子扩散速率与表面赝电容贡献率，缓解了材料储锂过程中的动力学限制。

关键词: 钙钛矿型高熵氧化物, 溶液燃烧法, 电化学, Li⁺掺杂, 负极材料

Abstract:

To address the intrinsic challenges of high-entropy oxides (HEOs) in energy storage applications, such as low intrinsic electrical conductivity and sluggish lithium ion transport kinetics, this study fabricated perovskite-type La(CoCrFeMnNiLix)_1/(5+x)O₃(x = 0, 0.2, 0.4, 0.6) HEO anode materials with varying Li⁺ doping contents via a solution combustion method. By regulating intrinsic defects including lattice distortion and oxygen vacancies, a significant enhancement in lithium storage performance was achieved. Electrochemical characterizations demonstrate that Li⁺ doping effectively optimizes the electrochemical properties of the materials. Specifically, the Li0.4 electrode exhibits outstanding rate capability and cyclic stability: it delivers a discharge specific capacity of 549.1 mAh g^-1 after 150 cycles at a current density of 200 mA g^-1, representing a 55.3% improvement compared to the undoped sample. Even at a high current density of 1000 mA g^-1, a reversible specific capacity of 503.6 mAh g^-1 is retained after 500 cycles (vs. 440 mAh g^-1 for the undoped sample). The excellent performance is attributed to the synergistic regulation of lattice distortion and high-concentration oxygen vacancies. On one hand, this regulation optimizes electron/ion transport pathways and increases active reaction sites; on the other hand, it significantly enhances lithium ion diffusion kinetics and the contribution of surface pseudocapacitance, thereby alleviating the kinetic limitations during the lithium storage process.

Key words: Perovskite-type high-entropy oxides, solution combustion synthesis, electrochemistry, Li⁺ doping, anode materials

中图分类号:

TM912

韦正兵, 徐世彪, 潘美伊, 尹飞龙, 韦丹, 贾洋刚, 檀杰, 冒爱琴. Li⁺掺杂诱导缺陷工程增强钙钛矿型高熵氧化物储锂性能[J]. 化工学报, DOI: 10.11949/0438-1157.20251156.

Zhengbing Wei, Shibiao Xu, Meiyi Pan, Feilong Yin, Dan Wei, Yanggang Jia, Jie Tan, Aiqin Mao. Li⁺ doping induced defect engineering for enhanced lithium storage performance in perovskite-type high-entropy oxides[J]. CIESC Journal, DOI: 10.11949/0438-1157.20251156.

图/表 10

图1 (a)样品的XRD图(插图为局部放大图)；(b)N2吸/脱附等温曲线及样品的孔径分布图；Li0(c1,c2)、Li0.4(d1,d2)和Li0.6(e1,e2)样品的SEM图；(f)Li0.4样品的EDS mapping图；Li0.4样品循环前的TEM图像(g)和循环150圈后的TEM图像(h)；循环前的高分辨率TEM(HRTEM)图像(i)和选区电子衍射(SAED)图(j)

Fig. 1 (a) XRD pattern of the sample (with the inset showing a locally magnified view); (b) N2 adsorption-desorption isotherm and pore size distribution curve of the sample; SEM images of Li0 (c1, c2), Li0.4 (d1, d2), and Li0.6 (e1, e2) samples; (f) EDS mapping images of the Li0.4 sample; TEM images of the Li0.4 sample before cycling (g) and after 150 cycles (h); High-resolution TEM (HRTEM) image before cycling (i) and selected area electron diffraction (SAED) pattern (j)

表1 BET比表面积（SBET）、BJH吸附累积孔隙体积（VBJH）、平均孔径（Daver.）和最可几孔径（Dmost）

Table 1 BET specific surface areas （SBET）， BJH adsorption cumulative pore volumes （VBJH）， and average pore diameters （Daver.）

Sample	S_BET (m² g^-1)	V_BJH (cm³ g^-1)	D_aver. (nm)	D_most/nm
Li0	18.337	0.063	13.849	3.367
Li0.2	16.739	0.079	18.861	2.780
Li0.4	16.719	0.076	18.235	2.539
Li0.6	14.445	0.065	18.121	2.764

图2 (a-g)Li0和Li0.4样品中各元素的XPS能谱，(h)EPR光谱和(i)四探针电导率

Fig. 2 (a-g) XPS energy spectra of each element in Li0 and Li0.4 samples, (h) EPR spectra, and (i) Four-probes couctivity

表2 XPS中阳离子价态浓度比

Table 2 Concentration ratios of cationic valence states in XPS

Samples	La³⁺	Co³⁺	Cr³⁺	Fe²⁺/Fe³⁺	Mn³⁺/Mn⁴⁺	Ni²⁺/Ni³⁺
Li0	1	1	1	57.2/42.8	66.3/33.7	57.8/42.2
Li0.4	1	1	1	55.4/44.6	56.2/43.4	59.7/40.3

图3 (a)Li0.4电极的循环伏安曲线；(b)充放电曲线；(c-f)Li0和Li0.4充放电时的微分容量图；(g-i) 不同电流密度下的循环性能及倍率性能

Fig. 3 (a) CV curves of the Li0.4 electrode; (b) Galvanostatic charge-discharge profiles; (c-f) Differential capacity plots of Li0 and Li0.4 electrodes during charge-discharge processes; (g-i) Cycling performance and rate capability at different current densities

表3 钙钛矿型负极材料性能对比

Table 3 Performance comparison of perovskite-type anode materials

Composition	Method	Cycling performance (mAh g^-1 ) (cycles)	Ref.
La (CoCrFeMnNiLix)₁_/(5+x) O₃	SCS	549.1(150) at 0.2 A g^-1； 503.6(500) at 1.0 A g^-1	This work
La(Co_0.2Cr_0.2Fe_0.2Mn_0.2Ni_0.2)O₃	SCS	569 (500) at 0.2 A g^-1； 325 (500) at 1.0 A g^-1	[13]
Gd(Co_0.2Cr_0.2Fe_0.2Mn_0.2Ni_0.2)O₃	SCS	403 (500) at 0.2 A g^-1 394 (500) at 1.0 A g^-1	[13]
Li_0.1(LiLaCaSrBa)Ti_0.9Al_0.1O₃	Mechanochemical	57 (100) at 0.1 A g^-1；	[26]
LaCoO₃/Co₃O₄-800	Hydrothermal method	550 (100) at 0.1 A g^-1	[27]

图4 (a)Li0.4电极在循环0, 3和50圈后的Nyquist图和等效电路 (b)在低频区域ω-1/2与Z'的关系图

Fig. 4 (a) Nyquist plots together with the equivalent circuit and (b) Plots of Z'vs. ω-1/2 of Li0.4 electrode before cycling, after 3 and 50 cycles

图5 (a)Li0.4电极在不同扫速下的CV曲线，(b)lg(ip)与lg(v)的关系曲线和(c)不同扫描速率下赝电容贡献率；(d)电极在不同扫描速率下赝电容贡献率汇总图，(e)ip与v1/2的关系图，(f)GITT测试过程中的充电/放电曲线和(g)充电/放电过程中的DLi+

Fig. 5 (a) CV curves of Li0.4 electrode at 0.1, 0.2, 0.5, 0.8, and 1.0 mV s-1 sweep rates, (b) lg(ip) vs. lg(v) curves and (c) Contribution ratios at different scan rates of the Li0.4 electrode; (d) Contribution ratios at different scan rates, (e) ipvsv1/2 curves of Li0.4 electrode, (f) Charge/discharge capacity curves during the GITT measurements and (g) DLi+ during the charge/discharge process of as-prepared electrodes

表4 电极循环0、3和50圈后的等效电路图参数

Table 4 Parameters of equivalent circuit diagrams of as-prepared electrodes before cycling， after 3 and 50 cycles

	R_s (Ω)			R_ct (Ω)			σ
	Pristine	3rd	50th	Pristine	3rd	50th	Pristine	3rd	50th
Li0	7.3	12.8	25.3	387.5	163.4	139.6	1299	1043	1722
Li0.2	13.9	5.1	12.8	201.2	187.1	95.6	707	532	1369
Li0.4	2.4	7.5	13.7	153.5	106.5	84.3	662	402	797
Li0.6	10.9	10.4	15.1	339.3	88.2	90.1	883	440	1653

表5 赝电容b值和循环伏安法DLi+

Table 5 The b value of pseudocapacitive and DLi+ obtained by cyclic voltammetry

Samples	b (Cathodic)	b (Anodic)	D_Li⁺/10^-10 cm² s^-1 (Cathodic)	D_Li⁺/10^-10 cm² s^-1 (Anodic)
Li0	0.81	0.91	0.8	2.3
Li0.2	0.85	0.78	1.8	6.2
Li0.4	0.86	0.78	2.5	7.6
Li0.6	0.86	0.76	2.7	6.7

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