水系锌锰电池电解液的电导性质研究

doi:10.19964/j.issn.1006-4990.2024-0013

Abstract

Abstract:

As one of the important components in aqueous Zn-Mn battery（AZMB），the electrolyte is not only a carrier of ion transport but also an active substance involved in electrochemical reactions，which has an important impact on AZMB cycle life and power density.The study of thermodynamic properties is conducive to determine optimal composition and molality under different working conditions in electrolytes，which optimizes battery design and improves performance.There have been research on the water system of VOSO₄ electrolytes，but there is a lack of relevant studies on MnSO₄ electrolytes.In this paper，the conductivity of manganese sulfate dilute solution with a molality range of 0.001~0.1 mol/kg was measured at 283.15~318.15 K.Limiting molar conductivity（Λ₀） and dissociation constant（K_d） of ［MnSO₄］⁰ ion pair in the dissociation process were obtained from the Fuoss method and Shedlovsky method.The calculative data was reliable compared with other divalent ions.The thermodynamic function of the dissociation process was obtained by fitting the equation of K_d and temperature，and the ionic interaction of Mn²⁺，SO₄^2-，and water molecules during the dissociation process was deeply discussed.The key step of the dissociation of ［MnSO₄］⁰ ion pair was the process in which water molecules were fixed around the hydration layer of Mn²⁺ to enhance the order of the system.This study provided basic theoretical support for analyzing the ionic structure and optimizing performance in manganese electrolytes.

Key words: conductivity, molar conductivity, dissociation constant, aqueous Zn-Mn battery, electrolyte

CLC Number:

TM911

QIN Ye, LIU Chang, HAN Song, WANG Shuo. Study on conductivity of electrolyte in aqueous Zn-Mn battery[J]. Inorganic Chemicals Industry, 2024, 56(11): 132-138.

Figures/Tables 12

Fig.1

Table 1

Table 2

Fig.2

Table 3

Fig.3

Table 4

Values of ［MnSO4］0 thermodynamic functions"

温度/K	ΔG⁰/ （kJ·mol^-1）	ΔS⁰/ ［J·（K·mol）^-1］	ΔH⁰/ （kJ·mol^-1）	$Δ C p 0$ / ［kJ·（K·mol）^-1］
283.15	13.43	-30.67	4.74	-2.026
288.15	13.68	-66.45	-5.47	-2.062
293.15	14.10	-102.23	-15.87	-2.098
298.15	14.70	-138.01	-26.45	-2.134
303.15	15.48	-173.79	-37.21	-2.169
308.15	16.44	-209.57	-48.14	-2.205
313.15	17.57	-245.35	-59.26	-2.241
318.15	18.89	-283.13	-70.55	-2.277

Table 4

Fig.4

Fig.5

Table 5

Limiting molar conductivity，ion radius，transference number and diffusion coefficient of Mn2+ and SO42-"

温度/K	$λ 0 +$ /（10^-4 S·cm²·mol^-1）	$λ 0 -$ /（10^-4 S·cm²·mol^-1）	$D 0 +$ /（10^-6 m²·s^-1）	$D 0 -$ /（10^-6 m²·s^-1）	D₀/（10^-6 m²·s^-1）	$t 0 +$	$t 0 -$	r_st/Å
283.15	38.23	53.68	4.83	6.79	5.65	0.416	0.584	3.28
288.15	43.90	61.81	5.65	7.95	6.61	0.415	0.585	3.28
293.15	49.58	70.47	6.49	9.23	7.62	0.413	0.587	3.30
298.15	58.31	80.00	7.76	10.65	8.98	0.422	0.578	3.16
303.15	65.57	89.47	8.88	12.11	10.24	0.423	0.577	3.13
308.15	84.60	99.90	11.64	13.75	12.61	0.459	0.541	2.69
313.15	119.40	111.00	16.70	15.53	16.09	0.518	0.482	2.10
318.15	166.20	122.90	23.61	17.46	20.07	0.575	0.425	1.65

Table 5

Fig.6

Table 6

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质量摩尔浓度/ （10^-3 mol·kg^-1）	电导率/（μS·cm^-1）
质量摩尔浓度/ （10^-3 mol·kg^-1）	283.15 K	288.15 K	293.15 K	298.15 K	303.15 K	308.15 K	313.15 K	318.15 K
1.009	153.4	175.9	198.8	225.8	249.8	290.0	351.4	406.8
2.002	279.0	313.8	351.8	391.4	432.4	479.4	530.2	595.6
2.998	387.0	436.0	487.0	544.0	594.6	652.4	714.2	787.6
4.007	493.0	554.8	621.8	687.8	751.4	819.0	891.8	967.4
4.999	590.0	664.0	743.6	822.2	897.8	980.0	1 065	1 145
6.003	687.0	775.4	865.0	953.8	1 041	1 130	1 222	1 318
7.001	779.4	873.8	975.8	1 078	1 177	1 278	1 385	1 487
7.995	867.4	972.8	1 086	1 199	1 307	1 416	1 535	1 649
9.004	954.8	1 074	1 194	1 315	1 435	1 560	1 688	1 814
10.08	1 037	1 163	1 306	1 439	1 571	1 700	1 839	1 970
20.12	1 802	2 028	2 258	2 484	2 698	2 922	3 152	3 358
39.96	3 100	3 450	3 840	4 224	4 572	4 946	5 306	5 676
60.01	4 238	4 740	5 272	5 792	6 266	6 764	7 278	7 738
80.01	5 290	5 916	6 572	7 212	7 814	8 444	9 060	9 612
100.0	6 248	7 012	7 776	8 492	9 250	9 980	10 702	11 368

质量摩尔浓度/ （10^-3 mol·kg^-1）	摩尔电导率/（S·cm²·mol^-1）
质量摩尔浓度/ （10^-3 mol·kg^-1）	283.15 K	288.15 K	293.15 K	298.15 K	303.15 K	308.15 K	313.15 K	318.15 K
1.009	76.03	87.24	98.71	112.22	124.32	144.56	175.49	203.56
2.002	69.70	78.43	88.01	98.03	108.45	120.43	133.44	150.20
2.998	64.56	72.77	81.35	90.98	99.58	109.44	120.02	132.63
4.007	61.53	69.28	77.72	86.07	94.15	102.79	112.13	121.88
4.999	59.03	66.47	74.50	82.47	90.18	98.60	107.37	115.68
6.003	57.24	64.64	72.18	79.68	87.07	94.72	102.60	110.87
7.001	55.68	62.46	69.81	77.18	84.39	91.84	99.70	107.26
7.995	54.26	60.89	68.02	75.22	82.07	89.11	96.72	104.14
9.004	53.04	59.68	66.41	73.22	80.06	87.17	94.48	101.71
10.08	51.47	57.76	64.91	71.58	78.28	84.85	91.93	98.70
20.12	44.79	50.43	56.20	61.90	67.33	73.04	78.93	84.26
39.96	38.79	43.20	48.13	53.00	57.45	62.25	66.90	71.71
60.01	35.33	39.53	44.01	48.41	52.45	56.71	61.13	65.12
80.01	33.08	37.01	41.16	45.22	49.06	53.10	57.10	60.68
100.0	31.26	35.10	38.96	42.60	46.47	50.22	53.95	57.43

温度/ K	Fuoss				Shedlovsky
温度/ K	Λ₀/（S·cm²·mol^-1）	K_d	r	10⁴s	Λ₀/（S·cm²·mol^-1）	K_d	r	10⁴s
283.15	87.8	0.005 32	0.985	4.46	91.9	0.003 49	0.997	2.33
288.15	100.7	0.004 83	0.979	4.86	105.7	0.003 17	0.995	2.79
293.15	114.0	0.004 56	0.976	4.81	120.0	0.002 98	0.994	2.78
298.15	130.7	0.003 87	0.970	5.26	138.3	0.002 54	0.991	3.27
303.15	146.0	0.003 53	0.965	5.38	155.0	0.002 32	0.989	3.47
308.15	172.1	0.002 56	0.943	7.39	184.5	0.001 72	0.972	5.72
313.15	212.8	0.001 63	0.896	11.10	230.4	0.001 15	0.931	10.00
318.15	267.4	0.001 02	0.899	11.70	289.0	0.000 78	0.927	10.80

样品	摩尔电导率/ （10^-4 S·cm²·mol^-1）	样品	缔合常数
Mn²⁺	58.31	MnSO₄	393.9
Cu²⁺	56.39	CuSO₄	248.6
Ni²⁺	54.02	NiSO₄	211.2
Co²⁺	53.64	CoSO₄	208.3
Zn²⁺	53.40	ZnSO₄	198.7
Mg²⁺	53.03	MgSO₄	157.2

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Study on conductivity of electrolyte in aqueous Zn-Mn battery

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