氨气气相还原法短程制备3.5价钒电解液

doi:10.11949/0438-1157.20250410

化工学报

• •

氨气气相还原法短程制备3.5价钒电解液

胡飞飞¹^,²(), 王程³, 王宝华⁴, 杜浩²^,⁵, 祁健⁴, 王海旭⁶, 王少娜²()

^1.大连大学环境与化学工程学院，辽宁省大连市 116020
^2.中国科学院过程工程研究所战略金属资源绿色循环利用国家工程研究中心，北京 100190
^3.北京集成电路装备创新中心有限公司，北京 100176
^4.承德钒钛新材料有限公司，河北承德 067102
^5.中国科学院大学国际学院，北京 100049
^6.河北河钢材料技术研究院有限公司，河北石家庄 052160

收稿日期:2025-04-17 修回日期:2025-06-12 出版日期:2025-07-08
通讯作者: 王少娜
作者简介:胡飞飞（2000—），女，硕士研究生，18247488929@163.com
基金资助:
国家重点研发计划项目(2024YFC3909504)

Preparation of 3.5-Valent Vanadium Electrolyte via Ammonia Gas-Phase Reduction

Feifei HU¹^,²(), Cheng WANG³, Baohua WANG⁴, Hao DU²^,⁵, Jian QI⁴, Haixu WANG⁶, Shaona WANG²()

^1.School of Environmental and Chemical Engineering, Dalian University, Dalian, Liaoning 116020, China
^2.National Engineering Research Center for Green Recycling of Strategic Metal Resources, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China
^3.Beijing Integrated Circuit Equipment Innovation Center Company Limited, Beijing 100176, China
^4.Chengde Vanadium and Titanium New Materials Company Limited, Chengde, Hebei 067102, China
^5.International School, University of Chinese Academy of Sciences, Beijing 100049, China
^6.Hebei HBIS Materials Technology Research Institute Company Limited, Shijiazhuang, Hebei 052160, China

Received:2025-04-17 Revised:2025-06-12 Online:2025-07-08
Contact: Shaona WANG

摘要/Abstract

摘要：

针对3.5价钒电解液传统化学还原-电化学还原制备工艺流程长、化学残留难脱除等问题，本论文提出氨气气相还原偏钒酸铵、多钒酸铵及五氧化二钒等原料一步获得3.5价钒氧化物-钒氧化物直接酸溶制备3.5价钒电解液新工艺。热力学计算与实验结果均表明，氨气还原偏钒酸铵、多钒酸铵及五氧化二钒均遵循V⁵⁺→V₆O₁₃→VO₂→V₄O₇→V₂O₃逐级还原原则，提高反应温度、氨气流量及延长反应时间均能促进五价钒的还原，在反应时间50min、氨气流量100mL/min条件下，在反应温度480 ℃、520 ℃和490 ℃分别还原偏钒酸铵、多钒酸铵和五氧化二钒，均可获得V浓度1.75mol/L以上、价态3.5±0.1的钒电解液，以偏钒酸铵和多钒酸铵为原料时电解液中钒浓度可达1.90mol/L以上；对三种原料还原后获得的电解液性能分析表明，以偏钒酸铵为原料导电性最优（离子电导率19.17S/m），分别较五氧化二钒（12.82S/m）和多钒酸铵（11.02S/m）体系提升了49.4%和73.9%。本论文提出的新工艺可避免3.5价钒电解液制备过程有机/化学还原剂残留，为全钒液流电池电解液制备技术的短流程发展提供了技术支撑。

关键词: 钒电解液, 氨气还原, 偏钒酸铵, 全钒液流电池, 多钒酸铵, 溶解度, 热力学性质

Abstract:

To address the issues of lengthy preparation process and difficult removal of chemical residues in traditional chemical reduction-electrochemical reduction methods for preparing 3.5-valent vanadium electrolyte, this study proposes an innovative process involving NH₃ gas-phase reduction of NH₄VO₃, (NH₄)₂V₆O₁₆, and V₂O₅ precursors to directly obtain 3.5-valent vanadium oxides, followed by dissolution to prepare 3.5-valent vanadium electrolyte. Both thermodynamic calculations and experimental results demonstrate that the NH₃ reduction of NH₄VO₃, (NH₄)₂V₆O₁₆, and V₂O₅ follows a stepwise reduction mechanism: V⁵⁺→V₆O₁₃→VO₂→V₄O₇→V₂O₃. Enhanced vanadium reduction was achieved by increasing reaction temperature, NH₃ flow rate, and prolonging reaction duration. Optimal conditions were established as: 50 min reaction time, 100 mL/min NH₃ flow rate, and 480 ℃ for NH₄VO₃ reduction; 520 ℃ for (NH₄)₂V₆O₁₆ reduction; and 490 ℃ for V₂O₅ reduction. These conditions yielded electrolytes with vanadium concentrations exceeding 1.75M and valence states of 3.5±0.1. Notably, NH₄VO₃ and (NH₄)₂V₆O₁₆ precursors achieved vanadium concentrations above 1.90M. Electrolyte performance analysis revealed that the NH₄VO₃ derived system exhibited superior conductivity (ionic conductivity 19.17 S/m), representing 49.4% and 73.9% enhancements over V₂O₅(12.83 S/m) and (NH₄)₂V₆O₁₆ (11.02 S/m) systems, respectively. This novel process eliminates organic/chemical reductant residues in electrolyte preparation, providing technical support for short process development of vanadium redox flow battery electrolyte production technologies.

Key words: vanadium electrolyte, ammonia reduction, NH₄VO₃, vanadium redox flow battery, (NH₄)₂V₆O₁₆, solubility, thermodynamic properties

中图分类号:

TQ152.1

胡飞飞, 王程, 王宝华, 杜浩, 祁健, 王海旭, 王少娜. 氨气气相还原法短程制备3.5价钒电解液[J]. 化工学报, DOI: 10.11949/0438-1157.20250410.

Feifei HU, Cheng WANG, Baohua WANG, Hao DU, Jian QI, Haixu WANG, Shaona WANG. Preparation of 3.5-Valent Vanadium Electrolyte via Ammonia Gas-Phase Reduction[J]. CIESC Journal, DOI: 10.11949/0438-1157.20250410.

图/表 15

图1 全钒液流电池工作原理示意图

Fig.1 Working principle diagram of vanadium flow battery

表1 钒电池正负极的反应［7］

Table 1 Reactions at the positive and negative electrodes in a vanadium battery

	电对反应	标准电势差
正极	$V O 2 + + 2 H + + e - ⇌ V O 2 + + H 2 O$	$E θ = 1.00 V$
负极	$V 3 + + e - ⇌ V 2 +$	$E θ = - O . 55 V$
总反应	$V O 2 + + V 3 + + H 2 O ⇌ V O 2 + + V 2 + + 2 H +$	$E θ = 1.26 V$

表1 钒电池正负极的反应［7］

Table 1 Reactions at the positive and negative electrodes in a vanadium battery

	电对反应	标准电势差
正极	$V O 2 + + 2 H + + e - ⇌ V O 2 + + H 2 O$	$E θ = 1.00 V$
负极	$V 3 + + e - ⇌ V 2 +$	$E θ = - O . 55 V$
总反应	$V O 2 + + V 3 + + H 2 O ⇌ V O 2 + + V 2 + + 2 H +$	$E θ = 1.26 V$

表 2 3.5价钒电解液制备工艺对比

Table 2 Comparison of 3.5-valent vanadium electrolyte preparation processes

	传统工艺	本研究新工艺
原料	五氧化二钒（¥71,000~¥72,000/MT）	偏钒酸铵（¥69,000/MT）多钒酸铵（¥67,000/MT）
工序	化学还原-电解-复配(V³⁺:V⁴⁺=1:1)	气相还原-溶解
能耗结构	电解能耗高，单位投资高 1.89-3.15 KWh/Kg V（电解过程）	焙烧热能为主，时间集中 0.21-0.29 KWh/Kg V（焙烧过程）
优点	技术成熟	工序简化、能耗低
局限性	还原剂/副产物残留、能耗高、流程长	氨气高温处理需严格安全措施

图2 电解液制备实验流程图

Fig.2 Experimental flowchart for electrolyte preparation

图3 （a）氨气还原钒氧化物反应过程吉布斯自由能； 300~500 ℃范围内产物XPS谱图：（b）氨气还原偏钒酸铵；（c）氨气还原多钒酸铵；（d）氨气还原五氧化二钒

Fig.3 (a) The Gibbs free energy of the reduction of vanadium oxide by ammonia gas; XPS spectra of products obtained at 300-500 °C: (b) NH3 reduction of NH4VO3; (c) NH3 reduction of (NH4)2V6O16; (d) NH₃ reduction of V2O5

图4 反应温度及氨气流量对偏钒酸铵还原产物及电解液中钒价态的影响；（a）20 mL/min NH3；（b）60 mL/min NH3；（c）100 mL/min NH3；（d）钒电解液平均价态变化

Fig.4 The effects of reaction temperatures and NH3 flow rates on the phase structure of NH4VO3 reduction products and vanadium valence states in the electrolyte; (a) 20 mL/min; (b) 60 mL/min; (c) 100 mL/min NH3; (d) changes of average valence state

图5 反应时间对偏钒酸铵还原产物物相及电解液总钒浓度、价态的影响；（a）还原产物的XRD图谱；（b）钒电解液平均价态及浓度变化

Fig.5 The effects of reaction time on the phase structure of reduction products and vanadium valence states in the electrolyte;(a) XRD patterns of the reduction products; (b) changes in average valence and concentration

图6 反应温度对多钒酸铵还原产物物相结构的影响；（a）还原产物的XRD图谱；（b）还原产物的FT-IR图谱

Fig.6 The effects of reaction temperature on the phase structure of (NH4)2V6O16 reduction products; (a) XRD patterns of the reduction products; (b) FT-IR patterns of the reduction products

图7 反应温度对多钒酸铵还原产物所制电解液的影响；（a）钒电解液紫外-可见分光光度计分析；（b）钒电解液平均价态及浓度变化

Fig.7 The effects of reaction temperature on the electrolyte prepared from (NH4)2V6O16 reduction products; (a) UV-Vis spectrophotometric analysis; (b) Variation of average valence state and concentration

图8 500~550 ℃多钒酸铵还原产物所制电解液平均价态及浓度变化

Fig.8 Average valence state and concentration of electrolytes prepared from (NH4)2V6O16 reduction products under 500~550 ℃

图9 反应温度对五氧化二钒还原产物物相结构的影响；（a）五氧化二钒还原产物的XRD图谱；（b）五氧化二钒还原产物的FT-IR图谱

Fig.9 The effects of reaction temperature on the phase structure of V2O5 reduction products; (a) XRD patterns of the V2O5 reduction products; (b) FT-IR patterns of the V2O5 reduction products;

图10 反应温度对五氧化二钒还原产物后电解液的影响；（a）钒电解液紫外-可见分光光度计分析；（b）钒电解液平均价态及浓度变化

Fig.10 The effects of reaction temperature on the electrolyte prepared from V2O5 reduction products; (a) UV-Vis spectrophotometric analysis; (b) Variation of average valence state and concentration

图11 450~500 ℃五氧化二钒还原产物后电解液平均价态及浓度

Fig.11 Average valence state and concentration of electrolytes prepared from V2O5 reduction products under 450~500 ℃

图12 3.5价钒电解液性能测试；（a）不同钒原料还原后获得的3.5价钒电解液循环伏安测试曲线；（b）电解液充放电循环效率分析图

Fig.12 Performance test results of 3.5 vanadium electrolytes prepared; (a) cyclic voltammetry of 3.5-valence vanadium electrolyte from different raw materials; (b) electrolyte charge-discharge cycling efficiency analysis chart

表3 不同钒原料还原后获得3.5价钒电解液循环伏安测试数据及电导率分析结果

Table 3 Electrochemical （CV） and conductivity analysis of 3.5-valent vanadium electrolytes derived from various vanadium materials

原料

氧化峰电流

（I_PO）

还原峰电流

（I_PR）

峰值电流比

（I_PO/I_PR）

峰值电位差

（ΔE_P）

电导率

(S/m)

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氨气气相还原法短程制备3.5价钒电解液

Preparation of 3.5-Valent Vanadium Electrolyte via Ammonia Gas-Phase Reduction

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