LiCl-KCl熔盐中Gd(Ⅲ)在Bi电极上的电化学行为及BixGdy金属间化合物的热力学数据

doi:10.7503/cjcu20170820

高等学校化学学报 ›› 2018, Vol. 39 ›› Issue (8): 1759.doi: 10.7503/cjcu20170820

LiCl-KCl熔盐中Gd(Ⅲ)在Bi电极上的电化学行为及Bi_xGd_y金属间化合物的热力学数据

姜涛¹(), 王宁¹, 彭述明¹, 李梅², 韩伟², 陈一东³

1. 中国工程物理研究院核物理与化学研究所, 绵阳 621999
2.哈尔滨工程大学材料科学与化学工程学院, 教育部超轻材料与表面技术重点实验室, 哈尔滨 150001
3.美国内华达大学拉斯维加斯分校机械工程系, 拉斯维加斯 89154-4027

收稿日期:2017-12-15 出版日期:2018-08-10 发布日期:2018-06-25
作者简介:联系人简介: 姜涛, 男, 博士, 副研究员, 主要从事核燃料循环与材料研究. E-mail: tjiang@caep.cn
基金资助:
国家自然科学基金(批准号: U1630102, 11675044, 11575047)、国家自然科学基金重大研究计划项目(批准号: 91426302, 91326113)和中央高校基本科研业务经费(批准号: HEUCF2016012)资助.

Electrochemical Behaviour of Gd(Ⅲ) on Bi Electrode and Thermodynamic Data of Bi_xGd_y Intermetallic Compounds in LiCl-KCl Molten Salts^†

JIANG Tao^1,^*(), WANG Ning¹, PENG Shuming¹, LI Mei², HAN Wei², CHEN Yitung³

1. Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang 621999, China
2. Key Laboratory of Superlight Materials and Surface Technology, Ministry of Education,College of Materials Science and Chemical Engineering, Harbin Engineering Universtiy, Harbin 150001, China
3. Department of Mechanical Engineering, Univeristy of Nevada Las Vegas, Las Vegas NV, 89154-4027, United States

Received:2017-12-15 Online:2018-08-10 Published:2018-06-25
Contact: JIANG Tao E-mail:tjiang@caep.cn
Supported by:
† Supported by the the National Natural Science Foundation of China(Nos. U1630102, 11675044, 11575047), the Major Research Plan of the National Natural Science Foundation of China(Nos. 91426302, 91326113) and the Fundamental Research Funds for the Central Universities, China(No. HEUCF2016012).

摘要/Abstract

摘要：

采用多种电化学技术研究了在723~823 K范围内LiCl-KCl熔盐中Gd(Ⅲ)在液态Bi电极和Bi膜电极上的电化学行为. 利用开路计时电位法估算了Bi-Gd金属间化合物(Bi₂Gd, BiGd, Bi₃Gd₄, Bi₃Gd₅)的活度、相对偏摩尔吉布斯自由能、生成吉布斯自由能、生成焓和生成熵等热力学数据. 通过恒电流和恒电位电解, 在液态Bi电极上制备了Bi-Gd合金, 并采用X射线衍射(XRD)和扫描电子显微镜-能量散射谱(SEM-EDS)表征了其结构. 在恒电流电解中所得金属间化合物为BiGd, 而在恒电位电解中所得金属间化合物为Bi₃Gd₅.

关键词: 电化学行为, 铋电极, 热力学性质, 铋-镉合金, 氯化物熔盐

Abstract:

Electrochemical behaviours of Gd(Ⅲ) were investigated on liquid Bi pool electrode and Bi film electrode in eutectic LiCl-KCl molten salts in the temperature range of 723—823 K by a series of electrochemical techniques. Moreover, the thermodynamic data, such as activities and relative partial molar Gibbs energies of Gd in the Bi-Gd alloys as well as the Gibbs energies, enthalpies and entropies of formation for Bi₂Gd, BiGd, Bi₃Gd₄ and Bi₃Gd₅ were calculated using open circuit chronopotentiometry. Galvanostatic and potentiostatic electrolysis were performed to prepare the Bi-Gd alloy on liquid Bi electrode. The alloy samples were characterized by X-ray diffraction(XRD) and scanning electronic microscopy-energy dispersive spectrometry(SEM-EDS). The results indicate that Bi-Gd alloys are comprised of BiGd and Bi₃Gd₅ phase, respectively.

Key words: Electrochemical behaviour, Bi electrode, Thermodynamic property, Bi-Gd alloy, Molten chloride

中图分类号:

O641
O643

TrendMD:

姜涛, 王宁, 彭述明, 李梅, 韩伟, 陈一东. LiCl-KCl熔盐中Gd(Ⅲ)在Bi电极上的电化学行为及Bi_xGd_y金属间化合物的热力学数据. 高等学校化学学报, 2018, 39(8): 1759.

JIANG Tao, WANG Ning, PENG Shuming, LI Mei, HAN Wei, CHEN Yitung. Electrochemical Behaviour of Gd(Ⅲ) on Bi Electrode and Thermodynamic Data of Bi_xGd_y Intermetallic Compounds in LiCl-KCl Molten Salts^†. Chem. J. Chinese Universities, 2018, 39(8): 1759.

图/表 11

Fig.1 Cyclic voltammograms under different conditionsa. LiCl-KCl melts on W electrode; b. LiCl-KCl-GdCl3(5.2×10-5 mol/mL) melts on W electrode; c. LiCl-KCl melts on liquid Bi electrode; d. LiCl-KCl-GdCl3(5.2×10-5 mol/mL) melts on liquid Bi pool electrode. Scan rate: 0.1 V/s, SW=0.314 cm2, SBi=0.2 cm2, T=773 K.

Fig.2 Cyclic voltammograms obtained in LiCl-KCl-GdCl3(5.2×10-5 mol/mL) melts on liquid Bi pool electrode at different scan rates(A) and relatioship between cathodic and anodic peak potentials with logarithm of scan rates(B)SBi=0.2 cm2, T=773 K.

Fig.3 Cyclic voltammograms under different conditions(A) LiCl-KCl-BiCl3(3.37×10-6 mol/mL) melts on W electrode(dotted curve); LiCl-KCl-BiCl3(3.37×10-6 mol/mL)-GdCl3(8.67×10-5 mol/mL) melts on pre-deposited Bi film electrode(solid line); (B) LiCl-KCl-BiCl3(3.37×10-6 mol/mL)-GdCl3(8.67×10-5 mol/mL) melts on pre-deposited Bi film electrode at different terminal potentials. Terminal potential/V: a. -2.25; b. -2.00; c. -1.80; d. 1.75. Scan rate=0.1 V/s, S=0.314 cm2, T=773 K.

Fig.4 Square wave voltammogram obtained in LiCl-KCl-BiCl3(3.37×10-6 mol/mL)-GdCl3(8.67×10-5 mol/mL) melts on pre-deposited Bi film electrodePotential step=1 mV, frequency=20 Hz, S=0.314 cm2, T=773 K.

Fig.5 Open circuit chronopotentiograms of different conditions(A) a. LiCl-KCl-GdCl3(8.67×10-5 mol/mL) melts on W electrode; b. LiCl-KCl-BiCl3(3.37×10-6 mol/mL) melts on W electrode; c. LiCl-KCl-BiCl3(3.37×10-6 mol/mL)-GdCl3(8.67×10-5 mol/mL) melts on pre-deposited Bi film electrode; (B) LiCl-KCl-BiCl3(3.37×10-6 mol/mL)-GdCl3(8.67×10-5 mol/mL) melts on pre-deposited Bi film electrode at different temperatures. Deposition potential=-2.5 V, deposition time=60 s, S=0.314 cm2, T=773 K.

Table 1 Thermodynamic properties of Gd in two-phase coexisting states at different temperatures

Plateau^*	T/K	E_eq/V(vs. Ag/AgCl)	ΔE/V[vs. Gd(Ⅲ)/Gd]	Δ $G ˉ Gd$ /[kJ·(mol Gd)^-1]	a_Gd
Ⅱ	723	-1.933±0.002	—	—	—
	748	-1.918±0.004	—	—	—
	773	-1.903±0.002	—	—	—
	798	-1.888±0.003	—	—	—
	823	-1.881±0.002	—	—	—
A	723	-1.106±0.003	0.827±0.005	-239.42±1.44	5.04×10^-18
	748	-1.093±0.002	0.825±0.006	-238.84±1.74	2.09×10^-17
	773	-1.081±0.002	0.822±0.004	-237.97±1.16	8.30×10^-17
	798	-1.071±0.003	0.817±0.006	-236.52±1.74	3.29×10^-16
	823	-1.067±0.003	0.814±0.005	-235.65±1.45	1.10×10^-15
B	723	-1.226±0.001	0.707±0.003	-204.68±0.87	1.63×10^-15
	748	-1.219±0.002	0.699±0.006	-202.36±1.74	7.38×10^-15
	773	-1.209±0.003	0.694±0.005	-200.91±1.45	2.65×10^-14
	798	-1.201±0.003	0.687±0.006	-198.89±1.74	9.57×10^-14
	823	-1.197±0.001	0.684±0.003	-198.02±0.87	2.70×10^-13
C	723	-1.441±0.001	0.492±0.003	-142.43±0.869	5.12×10^-11
	748	-1.439±0.001	0.479±0.005	-138.67±1.448	2.07×10^-11
	773	-1.438±0.002	0.465±0.004	-134.62±1.158	8.00×10^-10
	798	-1.436±0.002	0.452±0.005	-130.85±1.448	2.72×10^-9
	823	-1.433±0.001	0.448±0.003	-129.70±0.869	5.86×10^-9
D	723	-1.667±0.001	0.266±0.003	-77.00±0.869	2.73×10^-6
	748	-1.664±0.002	0.254±0.006	-73.53±1.74	7.32×10^-6
	773	-1.662±0.003	0.241±0.005	-69.77±1.45	1.93×10^-5
	798	-1.659±0.002	0.229±0.005	-66.30±1.45	4.57×10^-5
	823	-1.657±0.003	0.224±0.005	-64.85±1.45	7.66×10^-5

Table 1 Thermodynamic properties of Gd in two-phase coexisting states at different temperatures

Plateau^*	T/K	E_eq/V(vs. Ag/AgCl)	ΔE/V[vs. Gd(Ⅲ)/Gd]	Δ $G ˉ Gd$ /[kJ·(mol Gd)^-1]	a_Gd
Ⅱ	723	-1.933±0.002	—	—	—
	748	-1.918±0.004	—	—	—
	773	-1.903±0.002	—	—	—
	798	-1.888±0.003	—	—	—
	823	-1.881±0.002	—	—	—
A	723	-1.106±0.003	0.827±0.005	-239.42±1.44	5.04×10^-18
	748	-1.093±0.002	0.825±0.006	-238.84±1.74	2.09×10^-17
	773	-1.081±0.002	0.822±0.004	-237.97±1.16	8.30×10^-17
	798	-1.071±0.003	0.817±0.006	-236.52±1.74	3.29×10^-16
	823	-1.067±0.003	0.814±0.005	-235.65±1.45	1.10×10^-15
B	723	-1.226±0.001	0.707±0.003	-204.68±0.87	1.63×10^-15
	748	-1.219±0.002	0.699±0.006	-202.36±1.74	7.38×10^-15
	773	-1.209±0.003	0.694±0.005	-200.91±1.45	2.65×10^-14
	798	-1.201±0.003	0.687±0.006	-198.89±1.74	9.57×10^-14
	823	-1.197±0.001	0.684±0.003	-198.02±0.87	2.70×10^-13
C	723	-1.441±0.001	0.492±0.003	-142.43±0.869	5.12×10^-11
	748	-1.439±0.001	0.479±0.005	-138.67±1.448	2.07×10^-11
	773	-1.438±0.002	0.465±0.004	-134.62±1.158	8.00×10^-10
	798	-1.436±0.002	0.452±0.005	-130.85±1.448	2.72×10^-9
	823	-1.433±0.001	0.448±0.003	-129.70±0.869	5.86×10^-9
D	723	-1.667±0.001	0.266±0.003	-77.00±0.869	2.73×10^-6
	748	-1.664±0.002	0.254±0.006	-73.53±1.74	7.32×10^-6
	773	-1.662±0.003	0.241±0.005	-69.77±1.45	1.93×10^-5
	798	-1.659±0.002	0.229±0.005	-66.30±1.45	4.57×10^-5
	823	-1.657±0.003	0.224±0.005	-64.85±1.45	7.66×10^-5

Table 2 Formulas and results of calculated Gibbs free energies of formation for Bi-Gd intermetallic compounds

Intermetallic compound	Equation	T/K	Δ $G 0 — f$ /(kJ·mol^-1)
Bi₂Gd	Δ $G 0 — f$ (Bi₂Gd)=-3FΔE₁	723	-239.42±1.45
		748	-238.84±1.74
		773	-237.97±1.16
		798	-236.52±1.74
		823	-235.65±1.45
BiGd	Δ $G 0 — f$ (BiGd)=(1/2)[Δ $G 0 — f$ (Bi₂Gd)-3FΔE₂]	723	-222.05±1.16
		748	-220.60±1.74
		773	-219.44±1.30
		798	-217.70±1.74
		823	-216.84±1.16
Bi₃Gd₄	Δ $G 0 — f$ (Bi₃Gd₄)=3Δ $G 0 — f$ (BiGd)-3FΔE₃	723	-808.57±4.34
		748	-800.47±6.66
		773	-792.94±5.07
		798	-783.97±6.66
		823	-780.20±4.34
Bi₃Gd₅	Δ $G 0 — f$ (Bi₃Gd₅)=Δ $G 0 — f$ (Bi₃Gd₄)-3FΔE₄	723	-885.58±5.21
		748	-874.00±8.40
		773	-862.71±6.51
		798	-850.26±8.11
		823	-845.05±5.79

Table 2 Formulas and results of calculated Gibbs free energies of formation for Bi-Gd intermetallic compounds

Intermetallic compound	Equation	T/K	Δ $G 0 — f$ /(kJ·mol^-1)
Bi₂Gd	Δ $G 0 — f$ (Bi₂Gd)=-3FΔE₁	723	-239.42±1.45
		748	-238.84±1.74
		773	-237.97±1.16
		798	-236.52±1.74
		823	-235.65±1.45
BiGd	Δ $G 0 — f$ (BiGd)=(1/2)[Δ $G 0 — f$ (Bi₂Gd)-3FΔE₂]	723	-222.05±1.16
		748	-220.60±1.74
		773	-219.44±1.30
		798	-217.70±1.74
		823	-216.84±1.16
Bi₃Gd₄	Δ $G 0 — f$ (Bi₃Gd₄)=3Δ $G 0 — f$ (BiGd)-3FΔE₃	723	-808.57±4.34
		748	-800.47±6.66
		773	-792.94±5.07
		798	-783.97±6.66
		823	-780.20±4.34
Bi₃Gd₅	Δ $G 0 — f$ (Bi₃Gd₅)=Δ $G 0 — f$ (Bi₃Gd₄)-3FΔE₄	723	-885.58±5.21
		748	-874.00±8.40
		773	-862.71±6.51
		798	-850.26±8.11
		823	-845.05±5.79

Fig.6 Relatioship between standard Gibbs free energies of fomation for four Bi-Gd intermetallic compounds and temperatures

Table 3 Thermodynamic data of Bi-Gd intermetallic compounds in temperature range of 723—823 K

Intermetallic compound	Δ $H 0 — f$ / (kJ·mol^-1)	Δ $S 0 — f$ / (J·mol^-1·K^-1)
Bi₂Gd	-268.10±2.53	-39.39±3.27
BiGd	-387.34±3.74	-87.38±4.83
Bi₃Gd₄	-1400.22±19.96	-395.30±25.80
Bi₃Gd₅	-1568.07±27.40	-521.52±35.30

Table 3 Thermodynamic data of Bi-Gd intermetallic compounds in temperature range of 723—823 K

Intermetallic compound	Δ $H 0 — f$ / (kJ·mol^-1)	Δ $S 0 — f$ / (J·mol^-1·K^-1)
Bi₂Gd	-268.10±2.53	-39.39±3.27
BiGd	-387.34±3.74	-87.38±4.83
Bi₃Gd₄	-1400.22±19.96	-395.30±25.80
Bi₃Gd₅	-1568.07±27.40	-521.52±35.30

Fig.7 XRD pattern and SEM-EDS analysis of Bi-Gd alloy obtained in LiCl-KCl-GdCl3 melts by potentiostatic electrolysis(A) XRD pattern; (B) SEM image; (C) mapping analysis image of Bi; (D) mapping analysis image of Gd; (E) EDS spectrum of the framed area in (B). Electrolysis potential=-1.9 V, electrolysis time=4 h, Bi electrode, T=923 K.

Fig.8 XRD pattern and SEM-EDS analysis of Bi-Gd alloy obtained in LiCl-KCl-GdCl3 melts by galvanostatic electrolysis(A) XRD pattern; (B) SEM image; (C) mapping analysis image of Bi; (D) mapping analysis image of Gd; (E) EDS spectrum of the framed area in (B). Current intensity=-0.5 A, electrolysis time=5.5 h, Bi electrode, T=923 K.

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LiCl-KCl熔盐中Gd(Ⅲ)在Bi电极上的电化学行为及Bi_xGd_y金属间化合物的热力学数据

Electrochemical Behaviour of Gd(Ⅲ) on Bi Electrode and Thermodynamic Data of Bi_xGd_y Intermetallic Compounds in LiCl-KCl Molten Salts^†

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