聚苯并咪唑/聚乙烯吡咯烷酮复合质子交换膜的制备及钒液流电池性能

doi:10.7503/cjcu20180720

摘要/Abstract

摘要：

将聚苯并咪唑(PBI)与聚乙烯吡咯烷酮(PVP)共混, 制备了一系列PBI/PVP复合质子交换膜, 研究了不同PVP含量对PBI/PVP复合质子交换膜性能的影响. 研究结果表明, PVP的加入可有效提高PBI/PVP复合质子交换膜的吸水率及硫酸吸附量, 从而提高质子电导率, 与PBI原膜相比, PBI-PVP-5复合质子交换膜的结合酸含量可达2.47 mmol/g, 质子电导率达4.81 mS/cm, 选择性(3.12×10⁵ S·min/cm³)远高于原膜(1.12×10⁵ S·min/cm³). 电流密度为120 mA/cm²时, 电池的电压效率(VE)和能量效率(EE)均较PBI原膜提高了10%, 电池自放电时间长达307 h. PVP的加入为PBI系列钒液流电池隔膜提供了一个提高质子电导率的新思路.

关键词: 全钒液流电池, 聚苯并咪唑, 聚乙烯吡咯烷酮, 质子电导率, 电池效率, 质子交换膜

Abstract:

A series of proton exchange membranes(PEMs), based on polybenzimidazole(PBI) with different mass ratios of polyvinyl pyrrolidone(PVP) loadings, was prepared and investigated in vanadium redox flow battery(VRFB). The results showed that the addition of PVP effectively increased the water absorption, acid doping level(ADL) and proton conductivity of the PBI membrane. All membranes exhibit lower vanadium permeability than that of Nafion115 membrane, which were widely used in VRFB. Especially, the PBI/PVP-5 membrane exhibited higher bonded acid level of 2.47 mmol/g and proton conductivity of 4.81 mS/cm than that of PBI/PVP-0, as a result, the selectivity(3.12×10⁵ S·min·cm^-3) of PBI/PVP-5 is twice as much as the original PBI membrane(1.12×10⁵ S·min·cm^-3). At the current of 120 mA/cm², the voltage efficiency(VE=71.60%) and energy efficiency(EE=70.9%) of the cell employing PBI/PVP-5 increased about 10% compared with the original PBI membrane, respectively. The self-discharge time of VRFB assembled with PBI/PVP-5 reached to 307 h. All experimental results reported in this paper indicate that incorporation of PVP can increased water update(WU), ADL and proton conductivity of the PBI membrane at the same time. PBI/PVP proton exchange membranes, especially PBI/PVP-5 show promising prospects for VRFB applications.

Key words: Vanadium redox flow battery, Polybenzimidazole, Polyvinyl pyrrolidone, Proton conductivity, Cell efficiency, Proton exchange membrane

中图分类号:

O633.5

TrendMD:

宋西鹏, 刘金宇, 王丽华, 韩旭彤, 黄庆林. 聚苯并咪唑/聚乙烯吡咯烷酮复合质子交换膜的制备及钒液流电池性能. 高等学校化学学报, 2019, 40(7): 1543.

SONG Xipeng, LIU Jinyu, WANG Lihua, HAN Xutong, HUANG Qinglin. Preparation of Polybenzimidazole/Polyvinylpyrrolidone Proton Exchange Membranes for Vanadium Redox Flow Battery^†. Chem. J. Chinese Universities, 2019, 40(7): 1543.

图/表 14

Scheme 1 Structure of PBI

Scheme 2 Diffusion cell for measuring VO2+ permeability

Scheme 3 Assembly diagram of battery structure

Fig.1 FTIR spectra of PBI/PVP membranesa. PBI; b. PBI/PVP-5; c. PBI/PVP-10; d. PBI/PVP-15; e. PBI/PVP-20.

Fig.2 SEM cross-sectional images of PBI(A), PBI/PVP-5(B), PBI/PVP-10(C), PBI/PVP-15(D) and PBI/PVP-20(E)

Fig.3 Oxidative stability of PBI/PVP membranes (tested by Fenton reagent)a. PBI; b. PBI/PVP-5; c. PBI/PVP-10;d. PBI/PVP-15; e. PBI/PVP-20.

Fig.4 Mechanical properties of PBI/PVP membranesa. Nafion 115; b. PBI; c. PBI/PVP-5; d. PBI/PVP-10;e. PBI/PVP-15; f. PBI/PVP-20.

Table 1 Physicochemical properties of PBI/PVP membranes

Membrane	WU(%)	WU_doped(%)	ADL/(mmol·g^-1)	Free acid content/ (mmol·g^-1)	Bonded acid content/ (mmol·g^-1)	Thickness/μm
PBI	14.39	5.6	4.35	3.14	1.21	30
PBI/PVP-5	15.92	6.86	5.07	2.60	2.47	31
PBI/PVP-10	16.67	7.34	5.59	3.61	1.98	30
PBI/PVP-15	17.23	7.83	5.70	3.89	1.81	31
PBI/PVP-20	18.64	8.42	5.78	3.98	1.80	32

Fig.5 Vanadium ions concentration versus PBI/PVP membranes and Nafion115

Fig.6 Area resistance() and proton conductivity()(A) vanadium permeability() and proton selectivity() (B) of PBI/PVP membranesa. PBI; b. PBI/PVP-5; c. PBI/PVP-10; d. PBI/PVP-15; e. PBI/PVP-20.

Table 2 VRB single cell performance of PBI/PVP membranes

Membrane	50 mA/cm²			100 mA/cm²
Membrane	CE(%)	VE(%)	EE(%)	CE(%)	VE(%)	EE(%)
PBI	99.84	81.46	81.33	99.92	64.09	64/04
PBI/PVP-5	98.34	85.57	84.14	99.26	74.15	74.79
PBI/PVP-10	99.61	84.96	84.62	99.98	71.19	71.17
PBI/PVP-15	99.20	84.50	83.81	100.00	70.62	70.63
PBI/PVP-20	99.64	81.17	80.88	99.75	68.03	67.85

Fig.7 VRB efficiency assembled with PBI and PBI/PVP-5 at different current density(A) Columbic efficiency; (B) voltage efficiency; (C) energy efficiency.

Fig.8 Cyclic performance of VRB with PBI and PBI/PVP-5 at 100 mA/cm2 for 100 cycles(A) Columbic efficiency; (B) voltage efficiency; (C) energy efficiency.

Fig.9 Self-discharge curve of cell with PBI/PVP-5

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