不同碳源对磷酸锰铁锂高温循环过程中金属溶出的影响探究

doi:10.19964/j.issn.1006-4990.2024-0326

Abstract

Abstract:

The rapid degradation of battery capacity caused by the dissolving of iron and manganese metals during high-temperature cycling has been a challenge limiting the large-scale application of lithium manganese iron phosphate materials（LMFP） for long time.Different carbon sources were used to encapsulate and modify LMFP materials，in order to improve their ionic and electronic conductivity，and improve the problem of iron and manganese metal dissolution during high-temperature cycling.The results showed that when polyethylene pyrrolidone（PVP） was used as the carbon source，the average carbon layer thickness of the LMFP/C-1 sample was only 1.86 nm，and the uniformity was the best，with the highest degree of graphitization.The electrochemical characterization results of the coin-type half cell showed that the LMFP/C-1 sample coated with PVP as the carbon source had the highest discharge specific capacity at 0.1C rate，reaching 152.17 mA·h/g，and had the best rate and cycling performance.The electrochemical characterization results of the coin type full cell showed that the LMFP/C-1 sample had the highest discharge specific capacity at 0.1C rate under room temperature，which was 131.19 mA·h/g，and the discharge specific capacity after 100 cycles at 1.0C rate was still the highest among the three samples.However，under high temperature conditions，the LMFP/C-2 sample coated with glucose as the carbon source showed the highest discharge specific capacity after 100 cycles at 1C rate，and the total amount of Fe and Mn metals dissolution detected at the negative electrode after high temperature cycling was only 32.94 mg/L，indicating that glucose as the carbon source could effectively prevent metal dissolving during high temperature cycling and improve the high temperature cycling performance of LMFP.

Key words: carbon sources, lithium manganese iron phosphate, coin-type full-cell, high temperature cycling, metal dissolving

CLC Number:

TQ131.11

WANG Peng, RAO Yinan, HANG Jing, XIA Yuxin, WANG Zhaopei, WAN Yuanxin. Study on effect of different carbon sources on metal dissolving during high temperature cycles of lithium manganese iron phosphate[J]. Inorganic Chemicals Industry, 2025, 57(7): 64-72.

Figures/Tables 12

Fig.1

Fig.2

Fig.3

Table 1

Fig.4

Table 2

Table 3

Impedance fitting results and lithium ion diffusion coefficient results of samples"

样品	R₁/Ω	R₂/Ω	W₁/Ω	σ	D_Li $+$ /（cm²·s^-1）
LMFP/C-1	2.802	32.94	0.046	7.02	5.13×10^-12
LMFP/C-2	4.262	35.44	0.341	8.22	3.74×10^-12
LMFP/C-3	4.054	41.95	0.376	8.26	3.71×10^-12

Table 3

Fig.5

Table 4

Fig.6

Fig.7

Table 5

References 16

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样品	标尺/ nm	碳层厚度/nm								平均值/ nm	方差
样品	标尺/ nm	d₁	d₂	d₃	d₄	d₅	d₆	d₇	d₈	平均值/ nm	方差
LMFP/C-1	5	1.76	1.50	2.21	1.63	2.33	—	—	—	1.86	0.077
LMFP/C-1	20	2.05	2.19	1.92	1.70	1.90	1.59	1.43	2.02	1.86	0.077
LMFP/C-2	5	3.22	3.27	3.08	3.05	2.84	—	—	—	3.48	0.181
LMFP/C-2	20	2.99	3.70	3.92	3.58	4.30	3.84	3.92	3.52	3.48	0.181
LMFP/C-3	5	2.82	2.39	2.16	2.15	2.11	—	—	—	2.73	0.832
LMFP/C-3	20	3.71	3.42	5.28	2.43	2.94	2.01	1.90	2.12	2.73	0.832

样品	25 ℃，0.1C			25 ℃，1.0C
样品	充电比容量/ （mA·h·g^-1）	放电比容量/ （mA·h·g^-1）	库伦效率/%	充电比容量/ （mA·h·g^-1）	放电比容量/ （mA·h·g^-1）	库伦效率/ %
LMFP/C-1	152.26	152.17	99.94	152.00	143.46	94.38
LMFP/C-2	150.09	149.55	99.64	148.88	140.32	94.25
LMFP/C-3	150.56	148.45	98.60	148.22	137.92	93.05

样品	25 ℃、0.1C			45 ℃、0.1C
样品	充电比容量/ （mA·h·g^-1）	放电比容量/ （mA·h·g^-1）	库伦效率/%	充电比容量/ （mA·h·g^-1）	放电比容量/ （mA·h·g^-1）	库伦效率/ %
LMFP/C-1	132.41	131.19	99.08	140.33	134.14	95.59
LMFP/C-2	129.74	128.29	98.88	134.89	129.97	96.36
LMFP/C-3	130.68	129.49	99.09	133.26	126.99	95.29

样品	a/Å	b/Å	c/Å	V/Å³
LMFP/C-1循环前	4.725	10.386	6.059	297.34
LMFP/C-1循环后	4.711	10.374	6.038	295.09
LMFP/C-2循环前	4.725	10.401	6.064	298.01
LMFP/C-2循环后	4.708	10.374	6.029	294.45
LMFP/C-3循环前	4.722	10.398	6.061	297.59
LMFP/C-3循环后	4.779	10.057	5.959	286.38

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Inorganic Acid-Base-Salt Committee of CIESC

Study on effect of different carbon sources on metal dissolving during high temperature cycles of lithium manganese iron phosphate

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