Preparation and properties of Zr-MOF-NH2 and doped Nafion composite proton exchange membranes synthesized by microwaves
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摘要: 全钒液流电池要求质子交换膜具备优良的离子选择性和理化稳定性。本研究分别采用微波法和传统水热法制备UIO-66-NH2，利用浇筑法制备了UIO-66-NH2/Nafion复合质子交换膜，对膜的理化性质和电池性能进行系统研究。结果表明，UIO-66-NH2在复合膜内形成的氢键网络、酸碱对和自身孔道协同强化了膜的离子选择性。基于微波法(M/N)和传统水热法(T/N)的复合膜综合性能均优于纯树脂膜(P-N)。在掺杂量为3wt%时，M/N-3膜拉伸强度达到27 MPa，质子传导率和钒离子透过率分别为122.18 mS·cm−1和0.83×10−7 cm2·min−1，离子选择性为15.6×105 S·min·cm−3，约为P-N膜的30倍，且其电池能量效率达到83.8%~71.7% (100~200 mA·cm−2)，优于T/N-3膜(82.7%~71.0%)和P-N膜(79.4%~69.0%)。同时，该电池也显示出更优的循环稳定性和容量保持率。因此，微波法合成的UIO-66-NH2可有效改善质子交换膜的综合性能，在提高钒液流电池性能方面前景较好。Abstract: Vanadium liquid flow batteries require proton exchange membranes with excellent ion selectivity and physicochemical stability. In this work, UIO-66-NH2 was prepared by microwave and traditional hydrothermal method, respectively, and UIO-66-NH2/Nafion composite proton exchange membranes were prepared by the casting method, and the physicochemical properties of the membranes and the cell performance were systematically characterized. The results show that the hydrogen bonding network formed by UIO-66-NH2 within the composite membrane, acid-base pairs and its own pore size synergistically strengthened the ion selectivity of the composite membrane. The comprehensive performance of the composite membranes base on both microwave (M/N) and traditional hydrothermal (T/N) methods is superior to that of the pure resin membrane (P-N). At the addition amount of 3wt%, the tensile strength of the M/N-3 membrane reaches 27 MPa, the proton conductivity and vanadium ion permeability are 122.18 mS·cm−1 and 0.83×10−7 cm2·min−1, respectively, and the ion selectivity is 15.6×105 S·min·cm−3, which is about 30 times of that of the P-N membrane, and the cell energy efficiency of this membrane reaches 83.8%-71.7% (100-200 mA·cm−2), which is superior to T/N-3 membrane (82.7%-71.0%) and P-N membrane (79.4%-69.0%). The cell also shows superior cycling stability and capacity retention. Therefore, UIO-66-NH2 synthesized by microwave method can effectively improve the comprehensive performance of proton exchange membranes, which is promising in optimizing the performance of vanadium liquid flow batteries.
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图 1 微波合成氨基官能化的UIO-66 (UIO-66-NH2)及Nafion复合膜的制备过程示意图
Figure 1. Schematic diagram of the preparation process of UIO-66-NH2 and Nafion composite membrane
M-U66-NH2—UIO-66-NH2 prepared by microwave assisted method; UIO-66-NH2—Zr-MOF when the preparation method does not need to be distinguished; BDC-NH2—2-aminoterephthalic Acid; DMF—N, N-dimethylformamide; HAc—Acetic acid
图 2 不同温度下微波加热15 min ((a)~(d))、烘箱加热24 h (e)制备UIO-66-NH2的SEM图像及微波加热15 min样品的XRD图谱(f)
Figure 2. SEM images of UIO-66-NH2 by microwave heating for 15 min ((a)-(d)), oven heating for 24 h (e) and XRD patterns of UIO-66-NH2 by microwave heating for 15 min (f)
图 3 P-N (a)、M/N-1 (b)、M/N-3 (c) 膜的表面SEM图像；P-N (d)、M/N-1 (e)、M/N-3 (f)膜的截面SEM图像；M/N-3膜的表面EDS元素分布图((g) N；(h) Zr；(i) F；(j) S)
Figure 3. Surface SEM images of P-N (a), M/N-1 (b) and M/N-3 (c); Cross-section SEM images of P-N (d), M/N-1 (e) and M/N-3 (f); EDS element images of M/N-3 ((g) N; (h) Zr; (i) F; (j) S)
图 4 M/N-6 ((a), (c))和M/N-9 ((b), (d))膜的截面SEM图像
Figure 4. Cross-sectional SEM images of M/N-6 ((a), (c)) and M/N-9 ((b), (d))
图 5 M-U66-NH2、P-N膜和M/N-3膜的红外图谱
Figure 5. FTIR spectra of M-U66-NH2, P-N and M/N-3 membranes
图 6 复合膜的吸水率和溶胀率(a)、面电阻和质子传导率(b)、力学性能(c)和应力-应变曲线(d)
Figure 6. Water uptake and swelling ratio (a), area resistance and conductivity (b), mechanical properties (c) and stress-strain curves of different membranes (d)
N212—Nafion 212 commercial membrane, DuPont, USA
图 7 复合膜的钒离子渗透浓度(a)、钒离子渗透率和离子选择性(b)
Figure 7. Vanadium ion permeation concentration (a), vanadium ion permeability and ion selectivity (b) of composite membranes
图 8 不同膜所装配钒液流电池(VRBs)的库伦效率(CE) ((a), (d))、电压效率(VE) ((b), (e))和能量效率(EE) ((c), (f))
Figure 8. Coulombic efficiency (CE) ((a), (d)), voltage efficiency (VE) ((b), (e)) and energy efficiency (EE) ((c), (f)) of vanadium liquid flow battery (VRBs) assembled with different membranes
图 9 150 mA·cm−2电流密度下复合膜所装配电池的循环效率(a)、容量保持率(b)以及与报道性能的对比(c)
Figure 9. Cycle efficiency (a) and capacity retention (b) of composite membranes at 150 mA·cm−2, and comparisons with reported performance (c)
PBI—Polybenzimidazole; PS—Polystyrene; GO—Graphene oxide; SPEEK—Sulfonated poly(ether ether ketone); 2D-ZMs—Two-dimensional zeolite
表 1 复合质子交换膜的命名
Table 1. Naming of composite proton exchange membranes
Sample name Instruction M-U66-NH2 "M" represents microwave heating; "U66" refers to the metal-organic framework material UIO-66; Overall, it indicates the UIO-66-NH2 sample prepared by microwave heating. T-U66-NH2 "T" represents traditional oven heating; Overall, it indicates the UIO-66-NH2 sample prepared by oven heating. M/N-X "M/N" represents the composite membrane with M-U66-NH2 and Nafion resin; "X" represents the percentage content of M-U66-NH2 in the membrane. T/N-X "T/N" represents the composite membrane with T-U66-NH2 and Nafion resin; "X" represents the percentage content of T-U66-NH2 added to the membrane. P-N A pure, unmodified Nafion membrane N212 Commercial Nafion 212 membrane from DuPont (USA) 
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