单斜ZnP2负极材料的锂化机理及性能

doi:10.6023/A21120552

摘要/Abstract

过渡金属磷化物电位低且比容量高, 是有发展前景的锂离子电池(LIBs)负极材料. 其中, ZnP₂属于双活性负极材料, Zn与P都能与Li⁺发生反应, 储Li⁺性能更具有竞争力. 但是, 对于ZnP₂的锂化机理及产物尚不明确. 采用第一性原理计算和电化学测试方法研究了ZnP₂的电子性质和电化学性能, 通过理论计算和实验测试相结合阐述了ZnP₂的锂化机制. 首先, 以密度泛函理论(DFT)计算揭示了ZnP₂的锂化机理、Li⁺扩散路径、势垒和理论比容量(1477 mAh/g). 其次, 通过直流电弧等离子体法及固相烧结法合成ZnP₂, 并测试其首圈放电曲线, 显示放电容量为1439 mAh/g, 与理论计算结果相近. 此外, 薄膜X射线衍射(XRD)检测最终产物成分为LiZn和Li₃P, 与DFT计算结果一致.

关键词: LIBs, 负极材料, DFT, 直流电弧等离子体法, 锂化机制

Transition metal phosphides are promising anode materials for lithium ion batteries (LIBS) because of their low potential and high specific capacity. Among them, ZnP₂ is a dual active anode material, and both Zn and P can react with Li, which is more competitive in capacity. However, the lithiation mechanism and the reaction products of ZnP₂ are still unclear. In this work, the electronic and electrochemical properties of ZnP₂ were studied by first-principle calculations and electrochemical measurement. The combination of theoretical calculations and experimental tests demonstrated the lithiation mechanism of ZnP₂. Firstly, density functional theory (DFT) calculations revealed the lithiation reaction products, lithium diffusion path, diffusion barrier and theoretical lithium storage capacity (1477 mAh/g) of ZnP₂. The calculation of the binding energy proved that the formation energies of LiZn and Li₃P were thermodynamically lower than that of Li_nZnP₂. The charge density difference analysis showed that the Zn—P bonds and P—P bonds were gradually broken during the Li⁺ insertion process, which was accompanied by the formation of Li—P bonds and Li—Zn bonds, and these all confirmed the conversion reaction occurred after Li⁺ was inserted into ZnP₂. The calculation result of the density of states proved that ZnP₂ changed from a semiconductor to a conductor with the insertion of Li⁺. The diffusion energy barrier was higher than that of general layered materials, which will reduce the rate performance of LIBs. Secondly, ZnP₂ nanosheets were synthesized by the direct current (DC) arc plasma and solid phase sintering method. The electrochemical test showed that the rate performance and cycle performance were slightly worse, which proved the correctness of the diffusion barrier results. The discharge curve showed that the discharge capacity of the first cycle is similar to the theoretical calculation result, which is 1439 mAh/g. Finally, the components of the discharge products detected by the thin film X-ray diffraction (XRD) were LiZn and Li₃P, which were consistent with the DFT calculation results.

Key words: lithium ion battery (LIB), anode material, density functional theory (DFT), direct current (DC) arc plasma, lithiation process

引用此文

毕文超, 张琳锋, 陈健, 田瑞雪, 黄昊, 姚曼. 单斜ZnP₂负极材料的锂化机理及性能[J]. 化学学报, 2022, 80(6): 756-764.

Wenchao Bi, Linfeng Zhang, Jian Chen, Ruixue Tian, Hao Huang, Man Yao. Lithiation Mechanism and Performance of Monoclinic ZnP₂ Anode Materials[J]. Acta Chimica Sinica, 2022, 80(6): 756-764.

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图/表 11

Metal phosphide	P/M	Classification	Capacity/(mAh•g^–1)
FeP₂	>1 (高磷比)	单活性	1365^[31]
CuP₂	>1 (高磷比)	单活性	1280^[23]
GeP₅	>1 (高磷比)	双活性	2266^[28]
ZnP₂	>1 (高磷比)	双活性	1477
Ni₂P	≤1 (低磷比)	单活性	542^[26]
Sn₄P₃	≤1 (低磷比)	双活性	1255^[27]

表1. 常见磷化物负极分类及理论比容量

Table 1. Classification and capacity of common phosphating anode materials

图1. ZnP2结构主视图(a)和侧视图(b)

Figure 1. Front view (a) and side view (b) of ZnP2

Experimental/nm	Calculated/nm	Error/%
a=7.291×10^–6	a=7.31×10^–6	0.38
b=7.561×10^–6	b=7.604×10^–6	0.57
c=8.867×10^–6	c=8.886×10^–6	0.21

表2. ZnP2晶格常数对比

Table 2. Lattice constants of ZnP2

Super cell	1×1×1	2×1×1	2×2×1	2×2×2	3×3×3
E_ads/cell/eV	–101.254	–101.252	–101.253	–101.254	–101.240

表3. ZnP2不同超胞结合能对比

Table 3. Comparison of the binding energy of different super cell

Location	E_b/eV
L1	–1.74
L2	–1.52
L3	–1.63
L4	–1.63
L5	–0.68
L6	–0.84

表4. 不同嵌Li+位置结合能a

Table 4. Binding energy of Li+ in different positions

	Bond length/nm
	Zn(1)—P(1)	Zn(1)—P(2)	Zn(2)—P(3)	Zn(2)—P(4)	P(1)—P(3)	P(2)—P(4)
ZnP₂	0.237	0.244	0.244	0.237	0.223	0.223
LiZnP₂	0.236	0.244	0.235	0.262	0.221	0.230
Li₃ZnP₂	0.238	0.240	0.234	0.400	0.399	0.389
Li₅ZnP₂	0.536	0.226	0.231	0.406	0.675	0.389
Li₇ZnP₂	0.5639	0.461	0.250	0.411	0.529	0.403

表5. LinZnP2中的Zn—P键和P—P键键长(nm)

Table 5. Lengths (nm) of Zn—P bonds and P—P bonds in LinZnP2

图2. ZnP2电荷密度(a)侧视图、(b)主视图和(c)俯视图、(d) LiZnP2、(e) Li3ZnP2、(f) Li5ZnP2和(g) Li7ZnP2差分电荷密度主视图以及(h) LiZnP2结构差分电荷密度局部放大图. 为了分析ZnP2的电荷转移, (a)~(g)的isosurface设置为25 e/nm3, 为了更清楚地看到结构中的Li—Zn键和Li—P键, (h)的isosurface设置为1 e/nm3

Figure 2. (a) Side view, (b) front view and (c) top view of the charge density shape for ZnP2, front view of the charge density difference shape for (d) LiZnP2, (e) Li3ZnP2, (f) Li5ZnP2 and (g) Li7ZnP2, and (h) partial enlarged view of the differential charge density of the Li7ZnP2 To analyze the charge transfer of the ZnP2, the isosurface level of (a)~(g) is 25 e/nm3, and to see the Li—Zn bond and Li—P bond in the structure more clearly, the isosurface level of (h) is set to 1 e/nm3.

图3. LinZnP2态密度(DOS)图

Figure 3. Density of state (DOS) of LinZnP2

图4. (a)扩散路径1、(b)扩散路径2和(c)扩散路径3的主视图(左)和侧视图(右)以及(d)路径1、(e)路径2和(f)路径3扩散势垒

Figure 4. Front view (left) and side view (right) of (a) diffusion path 1, (b) diffusion path 2 and (c) diffusion path 3, and diffusion barriers for (d) path 1, (e) path 2 and (f) path 3

图5. (a, b)样品的SEM图和(c) X射线衍射图以及样品的(d) Zn 2p1/3和(e) P 2p XPS能谱图

Figure 5. (a, b) SEM images and (c) X-ray diffraction patterns, and XPS spectra at (d) Zn 2p1/3 and (e) P 2p of the samples

图6. (a)循环伏安测试图(CV)、(b) 20 mA/g电流密度下前三圈充放电曲线、(c)不同电流密度下的循环性能测试图、(d)不同电流密度下的倍率性能测试图、(e)充放电一次后样品的薄膜XRD图和(f) ZnP2嵌Li+反应机理图

Figure 6. (a) Cyclic voltammetry test chart, (b) charge and discharge curve of the first three circles at a current density of 20 mA/g, (c) cycle performance test curve at different current densities, (d) rate performance test at different current densities, (e) XRD of the sample after one charge and discharge and (f) Li+ intercalation mechanism of ZnP2

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单斜ZnP₂负极材料的锂化机理及性能

Lithiation Mechanism and Performance of Monoclinic ZnP₂ Anode Materials

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