基于霍爾-埃魯特電解法制備鋁合金技術研究進展

張城; 薛濟來; 劉軒; 李想; 朱駿; 劉翹楚; 錢義

doi:10.13374/j.issn2095-9389.2019.07.001

基于霍爾-埃魯特電解法制備鋁合金技術研究進展

doi: 10.13374/j.issn2095-9389.2019.07.001

張城¹,
薛濟來^1, ,,
劉軒¹,
李想^{1, 2},
朱駿^{1, 2},
劉翹楚^{1, 3},
錢義^{1, 4}

1.
北京科技大學冶金與生態工程學院, 北京 100083
2.
北京科技大學鋼鐵冶金國家重點實驗室, 北京 100083
3.
中國國際工程咨詢公司, 北京 100037
4.
國聯汽車動力電池研究院, 北京 100088

基金項目:

國家自然科學基金資助項目 51434005

國家自然科學基金資助項目 51704020

國家自然科學基金資助項目 51874035

詳細信息

通訊作者:
薛濟來, E-mail: jx@ustb.edu.cn

中圖分類號: TF821
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- PDF下載量: 57
- 被引次數: 0
出版歷程
- 收稿日期: 2018-06-28
- 刊出日期: 2019-07-01

Production of aluminum alloys in electrolysis cells based on Hall-Héroult process: a review

ZHANG Cheng¹,
XUE Ji-lai^{1
, ,},
LIU Xuan¹,
LI Xiang^{1, 2},
ZHU Jun^{1, 2},
LIU Qiao-chu^{1, 3},
QIAN Yi^{1, 4}

1.
School of Metallurgical and Ecological Engineering, University of Science and Technology Beijing, Beijing 100083, China
2.
State Key Laboratory of Advanced Metallurgy, University of Science and Technology Beijing, Beijing 100083, China
3.
China International Engineering Consulting Corporation, Beijing 100037, China
4.
China Automotive Battery Research Institute, Beijing 100088, China

More Information

Corresponding author: XUE Ji-lai E-mail: jx@ustb.edu.cn

摘要

摘要: 現代霍爾-埃魯特(H-H)法鋁電解槽規模大、工藝成熟, 利用該法電解制備鋁基合金具有明顯技術和經濟優勢. 目前國內外研究主要是在現有氟化物熔鹽體系中添加多種合金元素氧化物, 合理調節電解質成分和工藝參數, 借助共電沉積和欠電位機制, 成功制備出多種鋁基合金, 工業化試驗亦有初步成果. 本文綜合分析了上述進展及發展前景, 并指出在實現合金組成精準調控、合金產品成分均勻化、電解槽高電流效率運行等方面存在的問題, 旨在為相關研究提供參考.
- 鋁合金 /
- 鋁電解 /
- 霍爾-埃魯特法 /
- 金屬間化合物 /
- 分解電壓
Abstract: Modern large-scale Hall-Héroult (H-H) aluminum electrolysis cells have super high amperage and a well-developed process technology; thus, they present great technical and economic advantages for the production of Al-based alloys. Compared with the traditional alloy production methods, H-H-based processes have a great potential in improving product quality, simplifying production process, and reducing energy consumption. In this review, the major achievements in the production of various common aluminum alloys, such as Al-RE (rare earth metals), Al-Mg, and Al-Si/Ti alloys using H-H-based processes, were summarized from the domestic and international literature. The main properties of cryolite-based electrolyte systems that determine whether the alloy production can proceed smoothly by H-H process were first discussed based on previous research results. Studies on the electrolyte structure, melting point, and conductivity of the cryolite-based electrolytes with varying compositions were described in details. For producing Al-based alloys, the conventional fluorides electrolytes can be modified by adding various oxides of alloying metals. The electrolysis mechanisms of cathode co-deposition and underpotential deposition are usually utilized with the addition of multiple metals oxides, and the electrolyte composition and processing parameters are appropriately adjusted in H-H-based processes. Moreover, the potential distribution in the interfacial reaction processes during electrolysis for the alloying process in electrolyte is proposed based on the existing electrochemical data. In addition, some industrial trials showed promising results for the future development. At present, these trials, especially for Al-Si and Al-Ti alloys, indicate that the contents of alloying elements can be stabilized within a certain range by adjusting electrolyte compositions, current density, feeding cycle, and other parameters. There are, however, problems associated with the accurate control of alloy compositions, the homogenous quality in bulk alloy products, and the electrolysis cell operation with high current efficiency. Further research is needed to address these problems.
- aluminum alloy /
- aluminum electrolysis /
- Hall-Héroult process /
- intermetallic compound /
- decomposition voltage

HTML全文

圖 1 密度泛函理論計算結果.(a)Sc³⁺與F^-絡合物結構的幾何特征；(b)KScF₃和Al面的電子密度云圖^[18]

Figure 1. Results of DFT calculation: (a) geometrical characterization of Sc³⁺ and F^- complexes; (b) electron density cloud between KScF₃ and aluminum surface^[18]

下載: 全尺寸圖片幻燈片

圖 2 熔鹽電解鋁合金界面電化學反應過程及電勢分布示意圖

Figure 2. Schematic of the potentials in the interfacial reaction process of molten salt electrolysis for aluminum alloys

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圖 3 部分合金元素氧化物以及冰晶石電解質成分的熱力學分解電壓數值與溫度的關系

Figure 3. Theoretical decomposition voltages of alloying metal oxides and cryolitic components with varying temperature

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圖 4 Al-Sc合金掃描電鏡圖.(a)Sc質量分數為0.75%;(b)Sc質量分數為0.94%^[18]

Figure 4. SEM micrographs of Al-Sc alloys: (a) 0.75% Sc; (b) 0.94% Sc

下載: 全尺寸圖片幻燈片

表 1 部分合金元素金屬氧化物在冰晶石基熔鹽體系中的溶解度

Table 1. Solubility of selected oxides of alloying metals in cryolitic melts

合金元素氧化物	冰晶石基電解質組成(質量分數/%)	溫度/℃	溶解度/%	參考文獻
MgO	90NaF-NaCl	850	1.2	[22]
	NaCl-80Na₃AlF₆	850	1.9	[22]
	17.5NaCl-NaF-40Na₃AlF₆	850	2.1	[22]
Nd₂O₃	LiF-NdF₃-BaF₂	800~900	7~10	[23]
Sc₂O₃	7LiF-3Al₂O₃-Na₃AlF₆(CR=2.2)	900~980	3~5	[24]
	(3~9)ScF₃-Na₃AlF₆(CR=2.1)	950~990	4.01~5.68	[25]
	(CR=2.4~2.8)Na₃AlF₆-3MgF₂-3CaF₂-(1.5~4.5)Al₂O₃	960~980	1.95~4.75	[26]
CeO₂	5Al₂O₃-Na₃AlF₆(CR=2.7)	1040	1.65	[27]
Ce₂O₃	6Al₂O₃-Na₃AlF₆(CR=2.7)	1000	13.6	[27]
La₂O₃	5Al₂O₃-Na₃AlF₆(CR=2.7)	1000	14.3	[27]
TiO₂	3.5Al₂O₃-Na₃AlF₆	1020	5.2	[28]
SiO₂	Na₃AlF₆	1010	5	[29]
CuO	(1~9)Al₂O₃-Na₃AlF₆	1020	0.13~0.75	[30]
Cu₂O	(0.4~10)Al₂O₃-Na₃AlF₆	1020	0.2~0.28	[30]

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表 2 Al-RE金屬間化合物標準吉布斯自由能、偏摩爾吉布斯自由能以及欠沉積電位實驗值

Table 2. Experimental values of standard Gibbs free energies, partial molar Gibbs free energies of RE, and underpotential of Al-RE IMC

金屬間化合物	T/K	ΔG_f^?/ (kJ·mol^-1)	$ \Delta {{\tilde G}_{{\rm{RE}}}}/\left( {{\rm{kJ}} \cdot {\rm{mo}}{{\rm{l}}^{ - 1}}} \right) $	ΔE_UPD/V	參考文獻
Al₃Sc	723	-150.7	-150.7	0.521	[40]
Al₃Sc	773	-145.1	-145.5	0.501	[40]
Al₂Sc	723	-133.3.5	-98.4	0.340	[40]
Al₂Sc	773	-127.5	-92.4	0.319	[40]
AlSc	723	-93.2	-52.9	0.183	[40]
AlSc	773	-84.1	-40.7	0.141	[40]
AlSc₂	723	-108.4	-15.3	0.053	[40]
AlSc₂	773	-105.0	-21.6	0.075	[40]
PrAl_11/3	693	-180.65	-180.65	0.624	[49]
	723	-179.92	-179.92	0.622
	773	-177.66	-177.66	0.614
	823	-174.86	-174.86	0.604
Al₃Ho	673	-157.6	-157.6	0.544	[50]
	723	-155.4	-155.4	0.537
	773	-152.8	-152.8	0.528

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表 3 H-H法制備鋁基合金工業化實驗數據

Table 3. Industrial experimental data of Al-based alloys prepared by Hall-Héroult based process

合金體系	電解質組成/%	溫度/℃	電流強度/kA	槽電壓/V	合金元素質量分數/%	電流效率/%	參考文獻
Al-Ce	(1~3)Ce₂CO₃-Al₂O₃-Na₃AlF₆(CR= 2.35~2.45)	940~950	150	4.25~4.28	5.0~5.5	—	[56]
Al-Mn	Al₂O₃-Na₃AlF₆(CR=2.9)-MnO₂	958	24	5.1	1.0~1.8	82.9	[79]
Al-Mn	Al₂O₃-Na₃AlF₆(CR=2.8~2.9)-MnO₂	950	30	4.5~4.6	2.5~2.7	85	[80]
Al-Ti	Al₂O₃-Na₃AlF₆-(0.2~0.5)TiO₂	945~955	42	4.48~4.63	0.17~0.52	72~88	[74]
Al-Ti	Al₂O₃-Na₃AlF₆-(0.23~0.25)TiO₂	959~963	—	4.13	0.22~0.27	92~93	[10]
Al-Si	(2~2.5)Al₂O₃-Na₃AlF₆-(0.1~0.5)SiO₂	960	200	4.03~4.08	＜4.38	—	[77]
Al-Si-Ti	Al₂O₃-Na₃AlF₆-CaF₂-MgF₂-(0.87~ 1.47)SiO₂-(0.075~0.15)TiO₂	—	60	4.5	(4~10)Si- (0.39~0.91)Ti	73.86	[81]

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