電解水制氫技術及大電流析氧反應研究與展望

張唯怡; 張議潔; 王進偉; 趙強; 劉光; 李晉平

doi:10.13374/j.issn2095-9389.2022.09.20.005

電解水制氫技術及大電流析氧反應研究與展望

doi: 10.13374/j.issn2095-9389.2022.09.20.005

太原理工大學化學工程與技術學院氣體能源高效清潔利用山西省重點實驗室，太原 030024

基金項目: 國家自然科學基金面上項目（22075196, 21878204）；國家自然科學基金區域創新發展聯合基金項目（U22A20418）

詳細信息

通訊作者:
劉光，E-mail: liuguang@tyut.edu.cn

李晉平，E-mail: jpli211@hotmail.com

中圖分類號: TQ116.2+1
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- 文章訪問數: 457
- HTML全文瀏覽量: 277
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- 被引次數: 0
出版歷程
- 收稿日期: 2022-09-20
- 網絡出版日期: 2023-01-12
- 刊出日期: 2023-07-25

Research and perspectives on electrocatalytic water splitting and large current density oxygen evolution reaction

Shanxi Key Laboratory of Gas Energy Efficient and Clean Utilization, College of Chemical Engineering and Technology, Taiyuan University of Technology, Taiyuan 030024, China

More Information

Corresponding author: LIU Guang, E-mail: liuguang@tyut.edu.cn; LI Jin-ping, E-mail: jpli211@hotmail.com

摘要

摘要: 當今時代對可持續能源的迫切需求推動了可再生能源技術的不斷改進，其中氫能因其清潔環保且能量密度高而受到了科研人員廣泛關注。電解水制氫作為一種綠色環保的制氫方式，其陽極析氧反應（OER）的高能耗限制了電解水制氫技術的廣泛應用。近年來，高性能的OER催化劑的研究得到了長足發展，但催化劑的測試范圍小，且很少能夠連續工作數百小時，遠遠不能滿足實際應用的需求。為了更好的適用于工業應用，OER催化劑需要滿足更苛刻的測試環境，如在低過電位下提供大電流密度、在強氣體排放過程中維持穩定性和耐久性，因此開發在大電流密度下的高活性OER催化劑是當前工作的重中之重。結合大電流OER催化劑的研究進展，本文首先提出氫能是目前最有前途的能源之一，并調研了大電流密度下電催化劑的研究現狀。其次通過對OER機理進行分析，發現采取元素摻雜、界面工程、缺陷工程和形貌工程等措施可以提升催化劑在大電流密度下的活性。最后，對大電流析氧領域在工業發展中現階段存在的挑戰及未來發展方向進行了展望。
- 氫能 /
- 制氫 /
- 電解水 /
- 析氧反應 /
- 工業化 /
- 大電流密度
Abstract: With the consumption of fossil fuels and the deterioration of the ecological environment, the need for developing new, efficient, and sustainable sources of clean energy is urgent. The importance of “green hydrogen” in electrolytic water splitting has attracted worldwide attention not only from the scientific community but also from governments and industries. Hydrogen energy is considered an ideal alternative to fossil fuels because of its high energy density, environmental friendliness, and low pollution level. Hydrogen production from renewable energy sources using the electrolysis of water is the lowest carbon emission process of the many current hydrogen source options. The electrolytic water reaction is subdivided into two half-reactions, namely, the hydrogen evolution reaction (HER) at the cathode and the oxygen evolution reaction (OER) at the anode. The HER is a relatively simple two-electron reaction. Compared to the HER at the cathode, the OER at the anode is a four-electron transfer process with slower kinetics and higher energy barriers. It is the decisive step in the electrolytic water reaction, receiving considerable attention from scholars. Recently, considerable developments in the research of high-performance electrolytic water catalysts have been reported as successful; however, the catalysts have been tested on a very small scale, usually under laboratory conditions, and can rarely operate continuously for hundreds of hours, far from meeting the needs of practical applications. Industrial-level electrocatalytic hydrogen production requires catalysts that are highly active, cost-effective, and stable at high current densities; thus, a great deal of work has explored efficient and highly durable active electrocatalysts to overcome the kinetic barriers that inhibit the reaction, particularly for the complex four-electron reaction of the OER. In summary, catalysts for oxygen precipitation reactions at high current densities will be the focus of future research. This paper reviews the current status of hydrogen energy development and various hydrogen production methods at home and abroad, focusing on an analysis of electrolytic water hydrogen production technology and proposing the requirements under large-scale industrial applications. Studying the OER mechanism has revealed that the activity of catalysts at high current densities can be enhanced by the following strategies: heteroatom doping, defect engineering, interface engineering, in situ self-growth, etc. Finally, the challenges in the field of high-current oxygen analysis at this stage of industrial development and the future direction of development are presented.
- green hydrogen /
- hydrogen production /
- water electrolysis /
- oxygen evolution reaction /
- industrialization /
- large current density

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圖 1 HER反應機理示意圖. (a) 酸性電解質; (b) 堿性電解質

Figure 1. Schematic of the HER reaction mechanism: (a) acid electrolyte; (b) alkaline electrolyte

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圖 2 析氧反應機理示意圖. (a) 酸性環境; (b) 堿性環境

Figure 2. Diagram of the OER mechanism: (a) acidic environment; (b) alkaline environment

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圖 3 (a) 鈷摻雜NiO–Fe₃O₄@NiCo₂O₄ HNAs的制備示意圖; (b) 1 mol·L^–1 KOH溶液中鈷摻雜NiO–Fe₃O₄@NiCo₂O₄ HNAs、NiO–Fe₃O₄、NiCo₂O₄、IrO₂和NF的OER線性掃描伏安（LSV）曲線; (c) 鈷摻雜NiO–Fe₃O₄@NiCo₂O₄ HNAs在質量分數為30%的KOH溶液中過電位為270 mV時的計時電流曲線

Figure 3. (a) Synthetic schematic of Co-doped NiO–Fe₃O₄@NiCo₂O₄ HNAs; (b) OER linear sweep voltammetry (LSV) curves of the Co-doped NiO–Fe₃O₄@NiCo₂O₄ HNAs, NiO–Fe₃O₄, NiCo₂O₄, IrO₂, and NF in 1 mol·L^–1 KOH solution; (c) chronoamperometry curves of the Co-doped NiO–Fe₃O₄@NiCo₂O₄ HNAs in 30% (mass fraction) KOH at an overpotential of 270 mV

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圖 4 (a) CF/VMFP的合成過程示意圖; (b) 1 mol·L^–1 KOH溶液中CF/VMFP和對比樣的LSV曲線; (c) CF/VMFP在1 mol·L^–1 KOH溶液中電流密度為250 mA·cm^–2時的計時電位曲線

Figure 4. (a) Schematic for the synthesis process of CF/VMFP; (b) OER LSV curves of the CF/VMFP and othercatalysts in 1 mol·L^–1 KOH; (c) chronometric potential curve of CF/VMFP in 1 mol·L^–1 KOH at a current density of 250 mA·cm^–2

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圖 5 (a) Co₉S₈@Fe₃O₄的合成示意圖; (b) 1 mol·L^–1 KOH溶液中Co₉S₈@Fe₃O₄的OER過程中LSV曲線，插圖為不同催化劑在250和500 mA·cm^–2處的過電位; (c) Co₉S₈@Fe₃O₄和Co₉S₈在1 mol·L^–1 KOH中電流密度為500 mA·cm^–2時的計時電位曲線

Figure 5. (a) Synthetic schematic of the Co₉S₈@Fe₃O₄; (b) LSV curves of Co₉S₈@Fe₃O₄ for OER in 1 mol·L^–1 KOH. The inset shows overpotentials at 250 and 500 mA·cm^–2 for the corresponding catalysts; (c) chronometric potential curves of Co₉S₈@Fe₃O₄ and Co₉S₈ in 1 mol·L^–1 KOH at a current density of 500 mA·cm^–2

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圖 6 (a) Fe–Ni₃S₂電催化劑合成示意圖; (b) NiOOH的析氧反應的吉布斯自由能圖; (c) Ni_1–xFe_xOOH的析氧反應的吉布斯自由能圖

Figure 6. (a) Scheme for synthesis of Fe–Ni₃S₂ electrocatalyst; (b) Gibbs free-energy diagrams of OER for NiOOH; (c) Gibbs free-energy diagrams of OER for Ni_1–xFe_xOOH

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圖 7 (a) Co_1–xS/Co(OH)F/CC形貌示意圖; (b) Co_1–xS/Co(OH)F/CC的掃描電鏡圖; (c) S取代F原子形成Co(OH)F-S樣品的示意圖; (d) 1 mol·L^–1 KOH溶液中Co_1–xS/Co(OH)F/CC和對比樣的OER LSV曲線

Figure 7. (a) Schematic of the morphology of Co_1–xS/Co(OH)F/CC; (b) SEM images of Co_1–xS/Co(OH)F/CC; (c) schematic of S replacing F atoms to form a Co(OH)F-S sample; (d) OER LSV curves of the Co_1–xS/Co(OH)F/CC and contrast catalysts in 1 mol·L^–1 KOH

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圖 8 (a) KT-Ni(0)@Ni(Ⅱ)-TPA的合成方案; (b) Ni(0)@Ni(Ⅱ)-TPA, KT-Ni(0)@Ni(Ⅱ)-TPA, Ni(Ⅱ)-TPA, Ni foams, 和RuO₂/Ni foams在1 mol·L^–1 KOH中OER的LSV曲線; (c) KT結構的“超疏水性”特征在OER過程中促進氧氣氣泡釋放示意圖

Figure 8. (a) Scheme for the synthesis of KT-Ni(0)@Ni(Ⅱ)-TPA; (b) LSV curves of Ni(0)@Ni(Ⅱ)-TPA, KT-Ni(0)@Ni(Ⅱ)-TPA, Ni(Ⅱ)-TPA, Ni foams, and RuO₂/Ni foams for OER in 1 mol·L^–1 KOH; (c) schematic of the “superaerophobic” feature of the KT architecture for promoting the release of oxygen bubbles during OER

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圖 9 (a) FeWO₄–Ni₃S₂@C/NF合成示意圖; (b) FeWO₄–Ni₃S₂@C/NF的掃描電鏡圖; (c) 1 mol·L^–1 KOH溶液中FeWO₄–Ni₃S₂@C/NF在OER過程中LSV曲線

Figure 9. (a) Synthesis of FeWO₄–Ni₃S₂@C/NF; (b) SEM image of FeWO₄–Ni₃S₂@C; (c) LSV curves of the FeWO₄–Ni₃S₂@C/NF in 1 mol·L^–1 KOH duringOER process

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表 1 大電流密度下水分解電催化劑對比分析

Table 1. Summary of state-of-art electrocatalysts for high-current-density water splitting

Electrocatalysts	Electrolyte （KOH）/(mol·L^–1)	Overpotential/mV@current density/(mA·cm^–2)	Stability time/h	Ref.
NiCe@NiFe/NF	1	359@1000	20	31
NiO–Fe₃O₄@NiCo₂O₄	1	250@1000	100	33
(Ni,Fe)OOH	1	258@1000	120	34
Ni–Fe-OH@Ni₃S₂/NF	1	370@500	50	35
Ni–Fe-OH@Ni₃S₂/NF	1	469@1000	50	35
NiFe/NF	10	240@500	1.9	38
NiFe/NF	10	270@1000	—	38
NiCoV-LTH/NF	1	340@500	180	39
NiCoV-LTH/NF	1	373@1000	180	39
CF/VGSs/MoS₂/FeCoNi(OH)_x	1	225@500	30	40
CF/VGSs/MoS₂/FeCoNi(OH)_x	1	241@1000	—	40
Co₃O₄/Fe_0.33Co_0.66P	1	291@800	150	44
NiS₂/Fe-P	5	306@800	160	45
Co₉S₈@Fe₃O₄	1	350@500	120	46
Fe–Ni₃S₂	1	290@100	3500	51
Er_0.4Fe–MOF/NF	1	297@500	25	52
Er_0.4Fe–MOF/NF	1	326@1000	—	52
NiFe-LDH/NF-S	1	309@500	150	54
NiFe–NiSe@NIF	1	267@100	100	56
NiFe LDH/NiS	1	325@1000	—	62
FeWO₄–WO₃/NF	1	330@1000	100	66
KT-Ni(0)@Ni(II)-TPA	1	380@1500	80	69

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