Measurement and regression of solid-liquid binary equilibrium data for lithium battery additive FEC-VC system

doi:10.16085/j.issn.1000-6613.2023-1236

Abstract

Abstract:

The solid-liquid equilibrium data for binary mixtures of fluoroethylene carbonate-vinylene carbonate (FEC-VC) were determined by differential scanning calorimetry (DSC) for the lack of basic theoretical data in separation of lithium battery electrolyte additive by melt crystallization. The experimental data showed that the binary system presented a lowest eutectic point. On this basis, the activity coefficient data of binary system were calculated by activity coefficient method. With the data regression function of Aspen Plus process simulation software, the solid-liquid equilibrium data of the binary system were regressed using van laar, NRTL and Redlich-Kister models, and the regression parameters of each model were obtained. The binary solid-liquid equilibrium data were calculated by the models and the lowest eutectic type solid-liquid phase diagrams were plotted. The comparison of regression results of each model indicated that the deviation of van laar model was large, and the regression results of Redlich-Kister model were more in line with the experimental data with a standard deviation of equilibrium temperature of less than 0.005 and an average deviation of less than 1.0K. The solid-liquid equilibrium data and thermodynamics parameters were provided for the crystallization separation technology of FEC-VC system.

Key words: fluoroethylene carbonate, crystallization, thermodynamics, phase equilibria, activity coefficient, regression

摘要：

针对熔融结晶技术分离锂电池电解液添加剂存在缺少基础理论数据的问题，本文采用差示扫描量热法（DSC），测定了氟代碳酸乙烯酯（FEC）-碳酸亚乙烯酯（VC）二元固液平衡数据，实验数据表明该二元物系为低共熔型物系。在此基础上采用活度系数法进行分析计算，得到了二元体系活度系数数据。借助Aspen Plus流程模拟软件的数据回归功能，使用van laar、NRTL、Redlich-Kister模型对固液平衡数据进行回归，得到了各模型的回归参数。根据模型计算二元固液平衡数据，并绘制出相应的低共熔型二元固液相图。对各模型回归结果进行对比，结果显示van laar模型回归结果偏差较大，Redlich-Kister模型回归所得结果与实验数据较为相符，其平衡温度标准差小于0.005、平均偏差小于1.0K。为FEC-VC的结晶分离技术提供了固液平衡数据和热力学参数。

关键词: 氟代碳酸乙烯酯, 结晶, 热力学, 相平衡, 活度系数, 回归

CLC Number:

TQ013.1

XIANG Rui, AI Bo, WU Gaosheng, LI Yuzhe, ZONG Rui, XU Baoyun, DU Lijun. Measurement and regression of solid-liquid binary equilibrium data for lithium battery additive FEC-VC system[J]. Chemical Industry and Engineering Progress, 2024, 43(8): 4246-4252.

向瑞, 艾波, 吴高胜, 李瑜哲, 宗睿, 许保云, 杜丽君. 锂电添加剂FEC-VC二元体系固液平衡数据的测定及回归[J]. 化工进展, 2024, 43(8): 4246-4252.

Figures/Tables 7

x_FEC	T_e/K	T_m/K	ΔH_e/J·g^-1	ΔH_m/J·g^-1
0.00	260.60	298.75	0.00	136.80
0.10	260.94	290.36	27.58	73.98
0.20	261.05	280.85	58.83	9.45
0.30	260.84	271.56	82.88	1.23
0.33	260.55	—	110.23	0.00
0.36	260.67	—	135.98	0.00
0.40	260.63	—	145.80	0.00
0.43	260.97	—	141.70	0.00
0.46	260.39	—	129.40	0.00
0.50	260.42	—	118.30	0.00
0.60	260.49	274.43	81.51	2.05
0.70	260.30	281.42	60.24	7.90
0.80	260.24	287.60	29.94	37.84
0.90	260.29	292.70	6.68	99.35
1.00	260.60	300.47	0.00	170.70

T/K	x_FEC	γ_exp_i	x_VC	γ_exp_j
298.75	0.00	—	1.00	1.0000
290.36	0.10	7.7701	0.90	0.9689
280.85	0.20	3.0139	0.80	0.9241
271.56	0.30	1.5412	0.70	0.8889
260.60	0.40	0.8258	0.60	0.8333
274.43	0.60	0.8380	0.40	1.6427
281.42	0.70	0.8747	0.30	2.4896
287.60	0.80	0.9038	0.20	4.1608
292.70	0.90	0.9167	0.10	9.0669
300.47	1.00	1.0000	0.00	—

模型	van laar	NRTL	Redlich-Kister
a_ij	4.17	54.75	-7788.36
a_ji	3.51	100.00	-2667.08
b_ij	-544.50	-30000.00	28.98
b_ji	-544.50	30000.00	10.17
c_ij	—	0.20	-1916.35
c_ji	—	0.20	1096.96
d_ij	—	-0.0094	6.46
d_ji	—	-0.0094	-3.74
e_ij	—	32.12	—
e_ji	—	-69.03	—
f_ij	—	-0.46	—
f_ji	—	0.66	—

x_FEC	γ_exp	γ_{cal,van laar}	γ_cal,NRTL	γ_{cal,Redlich-Kister}
0.10	7.7701	5.2894	8.0760	7.6694
0.20	3.0139	3.3959	2.9216	3.0809
0.30	1.5412	2.3861	1.3827	1.5264
0.40	0.8258	1.8103	0.7556	0.8134
0.60	0.8380	1.2655	1.0926	0.8521
0.70	0.8747	1.1333	1.1086	0.9126
0.80	0.9038	1.0540	1.0733	0.9439
0.90	0.9167	1.0125	1.0260	0.9750
1.00	1.0000	1.0000	1.0000	1.0000

模型	σ	$d ¯$ /K
van laar	0.0558	13.0560
NRTL	0.0207	4.9843
Redlich-Kister	0.0042	0.9719

模型	σ	$d ¯$ /K
van laar	0.0558	13.0560
NRTL	0.0207	4.9843
Redlich-Kister	0.0042	0.9719

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