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摘要: 由于膜的吸水特性，高壓質子交換膜(PEM)制氫（尤其是差壓式，氫側高壓/氧側常壓）存在氫氣滲透問題，影響電解堆的運行安全與效率。基于菲克定律描述的滲透通量與滲透率、分壓差的關系，綜述了溫度/壓力、膜水合程度、氫氣分壓差對氫氣滲透的影響規律。在常規運行壓力范圍（3.5 MPa）內，擴散系數與溶解度主要受溫度影響，溫度升高則滲透率增大；氫氣滲透率隨膜水合程度的增加而增大；氫氣分壓差對滲透的影響表現出線性（滲透池環境）與非線性（電解制氫環境）兩種關系，非線性可能源于膜透水性提升與水通道結構改變引起的對流滲透。考慮到電解制氫實際工況存在電流，綜述了電流密度對氫滲透的影響，氫氣滲透率隨運行電流密度的升高而增大，氫過飽和是可能的影響機理，高電流密度下氫過飽和度升高，導致氫氣通過膜的滲透增加。Abstract: Hydrogen has the advantages of high energy density, no pollution, and long-term storage. As an important medium for the transformation of energy interconnection, it helps to promote the clean and efficient use of traditional fossil energy, support the large-scale development of renewable energy, and achieve large-scale deep decarbonization. With the excellent responsiveness to intermittent and fluctuating power supplies, proton exchange membrane (PEM) water electrolysis has been a research hotspot in the field of hydrogen production with renewable energy and will be one of the main technical routes for effective hydrogen supply in the future. The high-pressure operation of PEM electrolyzers has been successfully realized and commercialized, considering PEM’s outstanding mechanical strength and gas separation properties. However, due to the water-absorbing properties of the membrane, an important problem in high-pressure PEM water electrolysis (especially under differential pressure conditions and high pressure in the cathode compartment/atmospheric pressure in the anode compartment) is the permeation of hydrogen through the membrane, which affects safety and efficiency. In this article, the research progress of hydrogen permeation in PEM electrolysis was reviewed. First, the theory of permeation was introduced. Second, considering the relationship among the permeation flux, permeability, and partial pressure difference described by Fick’s law, the effects of temperature/pressure, hydration degree of the membrane, and partial pressure difference on hydrogen permeation were reviewed. In the normal operating pressure range (<3.5 MPa) for hydrogen production through PEM electrolysis, the diffusion coefficient and solubility are mainly affected by temperature, and the permeability increases with increasing temperature. The permeability of hydrogen in water is approximately 5–10 times that of a dry film, and the permeability increases with increases in the relative humidity of the membrane. The influence of partial pressure difference in hydrogen permeation shows a linear dependence in permeation cell and quadratic dependence in real electrolysis. The quadratic dependence may be attributed to the convective permeation caused by the increase in membrane water permeability and changes in the water channel. Third, considering the current in real operating conditions of electrolysis, the effect of current density on hydrogen permeation was reviewed. The permeability increases with the increase in current density, which may be attributed to the increase in hydrogen supersaturation in the cathode. At a high current density, the hydrogen concentration within the ionomer at the cathode catalyst particles become higher, and the high concentration gradient causes hydrogen to diffuse from cathode to anode.
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Key words:
- PEM water electrolysis /
- differential pressure /
- hydrogen permeation /
- permeability /
- current density
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圖 4 氫氣以不同路徑滲透通過PEM的示意圖（灰色區域代表固相, 藍色區域代表水相, 白色代表孔洞; 左側為干膜, 右側為濕膜）[14]
Figure 4. Descriptive sketch of the pathways for gas permeation through a segment of PEM exemplified for hydrogen molecules (The solid polymeric phase is depicted as the gray area, water as the blue area, and pores filled with gas as the white area; left: dry PEM; right: hydrated PEM)[14]
圖 5 Nafion膜三維結構模型的截面圖，圖中橫縱坐標表示200個網格單位，每個網格單位對應邊長為0.21 nm的立方體（灰色區域: 固相, 藍色區域: 水相, 綠色區域: 中間相）[27]
Figure 5. Two-dimensional cross section of the modeled three-dimensional cubic structure of Nafion with an edge length of 200 segments. One segment of the mesh corresponds to a cube with 0.21 nm edge length. (Gray area: solid phase; blue area: aqueous phase; green area: intermediate phase)[27]
圖 9 測量條件示意圖. (a) 水電解條件下測量; (b) 滲透池條件下測量(未施加電流)[28]
Figure 9. Schematic measurement conditions for (a) measurement during electrolysis and (b) measurement in a permeation cell without applying current[28]
Note: $ c_{{{\text{H}}_{\text{2}}}}^{\text{c}} $ is the dissolved hydrogen concentration in the cathode, mol·m-3; $ {S_{{{\text{H}}_{\text{2}}}}} $ is the solubility of hydrogen in water, mol·m-3·Pa-1; $ p_{{{\text{H}}_{\text{2}}}}^{\text{c}} $ is the hydrogen pressure in the cathode, Pa
久色视频
圖 11 陰極催化層離聚物中氫過飽和示意圖[33]
Figure 11. Sketch of the hydrogen supersaturation within the ionomer film of the cathode[33]
Note：$ c_{{{\text{H}}_{\text{2}}}}^ * $is the dissolved hydrogen concentration within the ionomer, mol·m−3; $ p_{{{\text{H}}_{\text{2}}}}^{\text{a}} $ is the hydrogen pressure in the anode, Pa; $ p_{{{\text{H}}_{\text{2}}}}^{\text{c}} $is the hydrogen pressure in the cathode, Pa; PTL is Porous transport layer
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