Design of high-energy-density LiFePO4 cathode materials

doi:10.19799/j.cnki.2095-4239.2023.0248

Abstract

Abstract:

Lithium iron phosphate (LiFePO₄) is one of the most widely used cathode materials in lithium-ion-based electric vehicles and energy storage batteries. To meet the market demand for high-energy-density lithium-ion batteries, high-energy-density LiFePO₄ products must be developed. According to the definition, energy density depends on the following three aspects: the voltage plateau, powder compacted density, and mass specific capacity. Based on electrochemistry and materials science, increasing the powder compacted density and mass specific capacity is a promising modification direction; however, voltage plateau is an intrinsic characteristic of LiFePO₄. Based on technical experience, market research reports, and previous research, the choice of raw materials, the modification of the sintering process, and particle gradation are the best modification methods for increasing powder compacted density. In the iron phosphate route, impurities are the primary issue in sintering processes; thus, different procedures for particle gradation are proposed. Considering mass specific capacity, the following strategies are proposed based on the intrinsic characteristics of LiFePO₄: nanosizing, carbon coating, elemental doping, defect control, and crystallographic preferred orientation. Moreover, nanosizing, carbon coating, and elemental doping are the most effective modification methods for increasing mass specific capacity. Usually, nanosizing and carbon coating are combined for increasing electronic conductivity, whereas elemental doping is mostly used for increasing Li-ion diffusion coefficient and preferred orientation. These modification methods are used in LiFePO₄ products available in the market and are confirmed by domestic battery factories. However, the energy density of LiFePO₄ has not yet been maximized; hence, additional methods for modifying the material properties and production processes need to be developed.

Key words: lithium iron phosphate, high energy density, powder compacted density, capacity, modified methods

CLC Number:

TM 911

Miao LI, Yongli YU, Jianyang WU, Min LEI, Henghui ZHOU. Design of high-energy-density LiFePO₄ cathode materials[J]. Energy Storage Science and Technology, 2023, 12(7): 2045-2058.

Figures/Tables 14

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Tab. 1

Atomic radius of doped elements and measured Li diffusion coefficients of LiFePO4[84]"

掺杂情况	原子半径/nm	D $L i +$ /(cm²/s)
未掺杂	0.092 (Fe²⁺ HS)，0.0785 (Fe³⁺ HS)	9.98×10^-14
V⁵⁺	0.068	6.93×10^-14
W⁶⁺	0.074	9.90×10^-14
Ti⁴⁺	0.0745	7.78×10^-14
Nb⁵⁺	0.078	4.90×10^-14
Zr⁴⁺	0.086	6.18×10^-14

Tab. 1

Fig. 11

Fig. 12

Fig. 13

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Design of high-energy-density LiFePO₄ cathode materials

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