高溫熔鹽體系惰性陽極與月壤電解制氧技術

寇明銀; 王明涌; 焦樹強

doi:10.13374/j.issn2095-9389.2021.10.08.001

高溫熔鹽體系惰性陽極與月壤電解制氧技術

doi: 10.13374/j.issn2095-9389.2021.10.08.001

寇明銀^{1, 2, 3},
王明涌^{1, 2, 3},
焦樹強^{1, 2, 3, ,}

1.
北京科技大學鋼鐵冶金新技術國家重點實驗室，北京 100083
2.
北京科技大學冶金與生態工程學院，北京 100083
3.
北京科技大學稀貴金屬綠色回收與提取北京市重點實驗室，北京 100083

基金項目: 國家自然科學基金資助項目（51725401）

詳細信息

通訊作者:
E-mail: sjiao@ustb.edu.cn

中圖分類號: TQ151.9
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- 被引次數: 0
出版歷程
- 收稿日期: 2021-10-08
- 網絡出版日期: 2021-11-15
- 刊出日期: 2021-12-24

Inert anode in a high-temperature molten salt system and oxygen generation by moon regolith electrolysis

KOU Ming-yin^{1, 2, 3},
WANG Ming-yong^{1, 2, 3},
JIAO Shu-qiang^{1, 2, 3
, ,}

1.
State Key Laboratory of Advanced Metallurgy, University of Science and Technology Beijing, Beijing 100083, China
2.
School of Metallurgical and Ecological Engineering, University of Science and Technology Beijing, Beijing 100083, China
3.
Beijing Key Laboratory of Green Recovery and Extraction of Rare and Precious Metals, University of Science and Technology Beijing, Beijing 100083, China

More Information

Corresponding author: E-mail: sjiao@ustb.edu.cn

摘要

摘要: 目前，熔鹽電化學冶金普遍采用炭素陽極，陽極CO₂產物是重要的碳排放源。若在高溫熔鹽體系中使用惰性析氧陽極，則可實現熔鹽電解過程低碳排放。因此，開發適用于熔鹽電解體系的惰性陽極至關重要，也是近年來國內外研究熱點。本文首先綜述了各種高溫熔鹽體系惰性陽極的研究進展，所涉及熔鹽體系包括：鋁電解氟化物鹽、CaCl₂熔鹽、碳酸鹽和熔融氧化物等。另外，近年來月球開發利用受到廣泛關注，太陽能驅動的月壤原位熔鹽電化學制氧，將是支撐人類未來月面生存氧氣需求的重要方法之一，故惰性析氧陽極不可或缺。因此，本文也簡要綜述了基于惰性陽極的月壤電解制氧技術。
- 碳減排 /
- 高溫熔鹽 /
- 惰性陽極 /
- 熔鹽電解 /
- 月壤制氧
Abstract: In 2020, China proposed to reach the peak of CO₂ emissions before 2030 and achieve carbon neutrality by 2060, which is the so-called “carbon peak and carbon neutrality” strategy. Due to strategic requirements, the metallurgical industry has the responsibility of reducing its CO₂ emission as it is one of the major CO₂ emitters. Therefore, it is imperative to develop low-carbon metallurgical technology. High-temperature molten salt electrochemical metallurgy uses electrons as the energy carrier and reaction driving force, having the advantages of cleanliness and high efficiency. It is the main extraction technology for aluminum, rare earth elements, alkali metal, and alkaline earth metals. Currently, carbon anodes are commonly used in molten salt electrochemical metallurgy, and CO₂ product is an important carbon emission source. If an inert oxygen evolution anode is used in a high-temperature molten salt system, then low-carbon emissions can be achieved in the molten salt electrolysis process. Therefore, the development of inert anodes suitable for molten salt electrolysis systems is very important, which has recently become a worldwide research hotspot. This article first reviewed the research progress of inert anodes in various high-temperature molten salt systems, including aluminum electrolytic fluoride salts, CaCl₂ molten salts, carbonates, and molten oxides. Meanwhile, the recent development and the utilization of the moon have received widespread attention. In the future construction of lunar bases, oxygen will be the basic prerequisite for human survival. Solar-driven in-situ oxygen production with molten salt electrochemistry from the moon regolith will be an important method in the future to support the oxygen demand for human survival on the moon. Hence, inert oxygen evolution anodes are essential. Therefore, this article also briefly summarized oxygen production technology by moon regolith electrolysis based on inert anodes.
- carbon emission reduction /
- high-temperature molten salt /
- inert anode /
- molten salt electrolysis /
- oxygen generation from moon regolith

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圖 1 現代鋁電解槽剖面圖^[3]

Figure 1. Sectional view of modern aluminum electrolysis bath^[3]

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圖 2 電解前后惰性陽極形貌圖. (a)電解前CaRuO₃；(b)電解后CaRuO₃；(c)電解后CaRu_xTi_1–xO₃；(d) 采用CaRuO₃ 惰性陽極的電解過程電流/氧氣隨時間變化圖^[42]

Figure 2. Morphology images of inert anodes before and after electrolysis: (a) CaRuO₃ before electrolysis; (b) CaRuO₃ after electrolysis; (c) CaRu_xTi_1–xO₃ after electrolysis; (d) current/oxygen–time profile for electrolysis using a CaRuO₃ anode^[42]

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圖 3 (a)100 h電解后TiB₂惰性陽極橫截面EPMA （Electron–probe micro analysis）結果；(b)膜I、II和III的XRD測試；(c)TiB₂陽極鈍化膜形成機理^[46]

Figure 3. (a) Electro–probe micro analysis of TiB₂ anode cross section after 100 h of electrolysis; (b) XRD tests of films I, II, and III; (c) formation mechanism of the TiB₂ anode passivation film^[46]

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圖 4 Ni₁₀Cu₁₁Fe三層膜形成示意圖^[49]

Figure 4. Schematic of the three-layer-coated Ni₁₀Cu₁₁Fe anode^[49]

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圖 5 熔融氧化物電解制備液態金屬和氧氣的示意圖^[58]

Figure 5. Schematic of the molten oxide electrolysis process involved in the electrolytic decomposition of a metal oxide into liquid metal and oxygen gas^[58]

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圖 6 Ir陽極在高硅氧化物（a，c）和高鈣氧化物（b，d）電解后的掃描電解圖及在高硅氧化物中恒電流電解過程中氣體出口氧氣含量隨時間變化（e）^[61]

Figure 6. SEM observations of iridium anode after electrolysis in high silica (a, c) and high calcia (b, d) and oxygen content of outlet gas in high–silica–content slag during constant–current electrolysis (e)^[61]

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圖 7 （a）Cr₉₀Fe₁₀的SEM圖；（b）Cr/Fe原子比EDS分析（沿圖7(a)中的虛線）；（c）Cr₉₀Fe₁₀電解質界面光學顯微圖；（d，e）Cr₉₀Fe₁₀表面XRD圖，靠近基體(d)及靠近電解質(e)；（f）恒電流電解過程中電壓、氧氣和氮氣含量（體積分數）隨時間的變化^[62]

Figure 7. (a) SEM image of Cr₉₀Fe₁₀; (b) Cr/Fe atomic ratio EDS analysis (along the dotted line in Fig.7(a)); (c) optical micrograph of the Cr₉₀Fe₁₀ electrolyte interface; (d, e) XRD diagrams of the Cr₉₀Fe₁₀ surface, which are close to the substrate (d) and electrolyte (e); (f) variation of the cell voltage and the oxygen and the nitrogen content (volume fraction) of the process gas during constant current electrolysis^[62]

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圖 8 月壤元素構成^[63]

Figure 8. Elemental composition of moon regolith^[63]

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圖 9 FFC法電解熔鹽電解制氧示意圖

Figure 9. Schematic of oxygen generation by FFC molten salt electrolysis

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表 1 鋁電解采用惰性陽極后的潛在優勢^[5]

Table 1. Potential advantages of adopting an inert anode in aluminum electrolysis^[5]

Environmental Protection	Cost	Energy Consumption	Process/Control	Safety/Health
① Reduce or eliminate CO₂ emissions; ② Eliminate the emissions of PFCs; ③ Eliminate the emissions of asphalt flue gas (polycyclic aromatic carbohydrates and polycyclic organics); ④ Eliminate the emissions of hydroxysulfides; ⑤ Eliminate dry coke powder and anode roasting paste dust emission; ⑥ Reduce the generation of waste lining; ⑦ Reduce HF emissions	①Reduce the anode cost; ②Improve the metal quality of the product; ③Increase the space utilization rate of the electrolytic cell; ④Increase the production capacity per unit volume of the electrolytic cell; ⑤Reduce operation manpower; ⑥More flexible cell structure design	①Improve the thermal efficiency of the electrolytic cell and reduce heat loss; ②Save energy consumption in the preparation of carbon anodes; ③Anode production is more energy efficient; ④Utilization in conjunction with wettable cathodes can greatly reduce electrode spacing, thereby reducing power consumption	①Carbon anode production plant is eliminated; ②Anode replacement frequency is reduced; ③The bottom of the anode is relatively flat, making control of the electrode spacing convenient	①Reduce anode replacement work; ②Electrolytic cell is more densely closed; ③Improve the working environment of the workshop

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