Lithiation Mechanism and Performance of Monoclinic ZnP2 Anode Materials

doi:10.6023/A21120552

Abstract

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

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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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Fig. & Tab. 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]

Table 1. Classification and capacity of common phosphating anode materials

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

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

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

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

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

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.

Figure 3. Density of state (DOS) of LinZnP2

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

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

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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单斜ZnP2负极材料的锂化机理及性能