季铵化杂萘联苯聚芳醚酮酮离子交换膜制备与性能
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摘要
离子交换膜是全钒氧化还原液流电池的主要部件之一,其选择性和稳定性在一定程度上决定了电池的寿命,而目前大多数离子交换膜存在选择性或稳定性欠佳的状况.为了制备全钒氧化还原液流电池用高选择性离子交换膜,本文将不同溴甲基含量(0.75～0.99,平均每摩尔重复结构单元含有溴甲基的摩尔数)的含溴甲基杂萘联苯聚醚酮酮(BPPEKK)通过溶液浇铸法制备基膜,之后在三甲胺水溶液中进行胺化得到季铵化杂萘联苯聚醚酮酮阴离子交换膜(QBPPEKK).测试了QBPPEKK的离子交换容量、吸水率、溶胀率、钒渗透系数和面电阻.随着BPPEKK溴甲基含量的增加,所得QBPPEKK膜的离子交换容量和含水率增加,而其面电阻和钒离子质量传递系数降低.将QBPPEKK膜组装于全钒氧化还原液流电池中,电池的电压效率(VE)和能量效率(EE)随着QBPPEKK膜离子交换容量的增加而上升;当BPPEKK的取代度为0.99时,所制得的阴离子交换膜为QBPPEKK90膜,由其组装成电池的EE为87.7%(电流密度为40m A/cm~2),大于同条件下Nafion117的数值(86.0%).在1.5mol/L的VO_2~+溶液中浸泡60d后, QBPPEKK膜的拉伸强度高于36 MPa、膜表面形貌没有明显变化、组装电池性能变化不大,结果表明QBPPEKK膜在VO_2~+溶液中表现出良好的稳定性.
As one of stationary energy storage device, all-vanadium redox flow battery(VRB) could effectively balance the relationship of electricity generation and demand side, in which interests are based on having features of high efficiency, flexible design, low cost and so on. Ion exchange membrane is one of the key components of VRB, separating redox-active ions and allowing the transfer of non-reaction species. Nafion series from Dupont company could ideally satisfy the requirements of high conductivity and good stability but facing the disadvantages of poor vanadium blocking ability in VRB. Modified Nafion membranes partially conquered the problem of poor ion selectivity but still suffering from high cost. Cationic exchange membranes prepared from non-fluorinated polymers have lower vanadium ion permeability and cost while cationic exchange groups hinder the further improvement of vanadium ion blocking. On the contrary, anionic exchange membranes(AEMs) exhibit low vanadium ion diffusion coefficient because of Donnan exclusive effection. It is much of importance to explore new AEMs. And the lifetime of the VRB cell depends on the selectivity and stability of the membranes to some degree. However, most of ion exchange membranes for VRB application showed low selectivity or stability. In order to improve the selectivity of ion exchange membranes, poly(phthalazinone ether ketone ketone) containing bromomethyl moieties(BPPEKK) with varied content of bromomethyl were dissolved to prepare BPPEKK base membranes using solution casting method. Quaternized poly(phthalazinone ether ketone ketone)(QBPPEKK) anion-exchange membranes were prepared from the amination of BPPEKK membranes in trimethylamine aqueous solutions. The measured ion exchange capacity(IEC) values of QBPPEKK membranes were in the range of 1.15–1.51 mmol/g, which were lower than the theoretical IEC(IEC_T) values. The result indicated the incomplete amination reaction of bromomethyl groups with trimethylamine. Properties of QBPPEKK membranes including water uptake, swelling ratio, area resistance and vanadium ion permeability were investigated. Water uptake and swelling ratio of QBPPEKK membranes increased with the increase in content of bromomethyl in BPPEKK, while area resistance and vanadium ion permeability decreased. The vanadium ion mass transfer coefficient of QBPPEKK membranes was in the range of 2.3×10~(-5)–5.0×10~(-5) cm/min, less than that of Nafion 117 membrane(11.9×10~(-5) cm/min). QBPPEKK membranes showed much lower vanadium ion permeability than Nafion 117. VRB with each QBPPEKK membrane showed higher columbic efficiency(CE) than the battery with Nafion117 membrane. QBPPEKK membrane with higher IEC exhibited higher voltage efficiency and energy efficiency(EE). When the content of bromomethyl reached 0.99, the VRB with QBPPEKK90 membrane had EE of 87.7%(current density: 40 mA/cm~2), higher than that of Nafion117 membrane(86.0%). When the charge-discharge current density increased from 20 to 80 mA/cm~2, the CE of VRB with QBPPEKK90 membrane increased from 97.1% to 99.0%, and EE of VRB cell with QBPPEKK90 decreased from 91.1% to 80.2%. After QBPPEKK membranes were immersed in VO_2~+ solution for 60 d, the tensile strength of the membranes was more than 36 MPa, which was lower than that of the original QBPPEKK90 membrane. There were no significant changes on microstructure of QBPPEKK membrane after the membrane had been immersed into 1.5 mol/L VO_2~+ solutions for 60 d. Compared with the original QBPPEKK90 membrane, CE changed slightly and EE decreased 1.4% at the charge-discharge current density ranging from 20 to 60 mA/cm~2 after the membrane was immersed in VO_2~+ solution for 60 d. The results suggested that QBPPEKK membranes showed good chemical stability.
As one of stationary energy storage device, all-vanadium redox flow battery(VRB) could effectively balance the relationship of electricity generation and demand side, in which interests are based on having features of high efficiency, flexible design, low cost and so on. Ion exchange membrane is one of the key components of VRB, separating redox-active ions and allowing the transfer of non-reaction species. Nafion series from Dupont company could ideally satisfy the requirements of high conductivity and good stability but facing the disadvantages of poor vanadium blocking ability in VRB. Modified Nafion membranes partially conquered the problem of poor ion selectivity but still suffering from high cost. Cationic exchange membranes prepared from non-fluorinated polymers have lower vanadium ion permeability and cost while cationic exchange groups hinder the further improvement of vanadium ion blocking. On the contrary, anionic exchange membranes(AEMs) exhibit low vanadium ion diffusion coefficient because of Donnan exclusive effection. It is much of importance to explore new AEMs. And the lifetime of the VRB cell depends on the selectivity and stability of the membranes to some degree. However, most of ion exchange membranes for VRB application showed low selectivity or stability. In order to improve the selectivity of ion exchange membranes, poly(phthalazinone ether ketone ketone) containing bromomethyl moieties(BPPEKK) with varied content of bromomethyl were dissolved to prepare BPPEKK base membranes using solution casting method. Quaternized poly(phthalazinone ether ketone ketone)(QBPPEKK) anion-exchange membranes were prepared from the amination of BPPEKK membranes in trimethylamine aqueous solutions. The measured ion exchange capacity(IEC) values of QBPPEKK membranes were in the range of 1.15–1.51 mmol/g, which were lower than the theoretical IEC(IEC_T) values. The result indicated the incomplete amination reaction of bromomethyl groups with trimethylamine. Properties of QBPPEKK membranes including water uptake, swelling ratio, area resistance and vanadium ion permeability were investigated. Water uptake and swelling ratio of QBPPEKK membranes increased with the increase in content of bromomethyl in BPPEKK, while area resistance and vanadium ion permeability decreased. The vanadium ion mass transfer coefficient of QBPPEKK membranes was in the range of 2.3×10~(-5)–5.0×10~(-5) cm/min, less than that of Nafion 117 membrane(11.9×10~(-5) cm/min). QBPPEKK membranes showed much lower vanadium ion permeability than Nafion 117. VRB with each QBPPEKK membrane showed higher columbic efficiency(CE) than the battery with Nafion117 membrane. QBPPEKK membrane with higher IEC exhibited higher voltage efficiency and energy efficiency(EE). When the content of bromomethyl reached 0.99, the VRB with QBPPEKK90 membrane had EE of 87.7%(current density: 40 mA/cm~2), higher than that of Nafion117 membrane(86.0%). When the charge-discharge current density increased from 20 to 80 mA/cm~2, the CE of VRB with QBPPEKK90 membrane increased from 97.1% to 99.0%, and EE of VRB cell with QBPPEKK90 decreased from 91.1% to 80.2%. After QBPPEKK membranes were immersed in VO_2~+ solution for 60 d, the tensile strength of the membranes was more than 36 MPa, which was lower than that of the original QBPPEKK90 membrane. There were no significant changes on microstructure of QBPPEKK membrane after the membrane had been immersed into 1.5 mol/L VO_2~+ solutions for 60 d. Compared with the original QBPPEKK90 membrane, CE changed slightly and EE decreased 1.4% at the charge-discharge current density ranging from 20 to 60 mA/cm~2 after the membrane was immersed in VO_2~+ solution for 60 d. The results suggested that QBPPEKK membranes showed good chemical stability.
引文
1 Wang W,Luo Q T,Li B,et al.Recent progress in redox flow battery research and development.Adv Funct Mater,2013,23:970-986
2 Kear G,Shah A A,Walsh F C.Development of the all-vanadium redox flow battery for energy storage:A review of technological,financial and policy aspects.Int J Energy Res,2012,36:1105-1120
3 Soloveichik G L.Electrochemistry:Metal-free energy storage.Nature,2014,505:163-165
4 Skyllas-Kazacos M,Kazacos G,Poon G,et al.Recent advances with UNSW vanadium-based redox flow batteries.Int J Energy Res,2010,34:182-189
5 Zhang H M,Zhao P,Zhou H T,et al.Vanadium redox flow battery for energy storage(in Chinese).Energy Technol,2005,26:23-26[张华民,赵平,周汉涛,等.钒氧化还原液流储能电池.能源技术,2005,26:23-26]
6 Wen Y H,Zhang H M,Qian P,et al.Study on ion exchange membrane as a separator for all-vanadium redox flow battery(in Chinese).Battery,2005,35:414-416[文越华,张华民,钱鹏,等.离子交换膜全钒液流电池的研究.电池,2005,35:414-416]
7 Ding C,Zhang H M,Li X F,et al.Vanadium flow battery for energy storage:Prospects and challenges.J Phys Chem Lett,2013,4:1281-1294
8 Parasuraman A,Lim T M,Menictas C,et al.Review of material research and development for vanadium redox flow battery applications.Electrochim Acta,2013,101:27-40
9 Li X F,Zhang H M,Mai Z S,et al.Ion exchange membranes for vanadium redox flow battery(VRB)applications.Energy Environ Sci,2011,4:1147-1160
10 Lu W J,Yuan Z Z,Zhao Y Y,et al.Porous membranes in secondary battery technologies.Chem Soc Rev,2017,46:2199-2236
11 Prifti H,Parasuraman A,Winardi S,et al.Membranes for redox flow battery applications.Membranes,2012,2:275-306
12 Yu L H,Lin F,Xu L,et al.A recast Nafion/graphene oxide composite membrane for advanced vanadium redox flow batteries.RSC Adv,2016,6:3756-3763
13 Teng X G,Zhao Y T,Xi J Y,et al.Nafion/organically modified silicate hybrids membrane for vanadium redox flow battery.J Power Sources,2009,189:1240-1246
14 Xi J Y,Wu Z H,Qiu X P,et al.Nafion/SiO2 hybrid membrane for vanadium redox flow battery.J Power Sources,2007,166:531-536
15 Luo Q T,Zhang H M,Chen J,et al.Modification of Nafion membrane using interfacial polymerization for vanadium redox flow battery applications.J Membr Sci,2008,311:98-103
16 Winardi S,Raghu S C,Oo M O,et al.Sulfonated poly(ether ether ketone)-based proton exchange membranes for vanadium redox battery applications.J Membr Sci,2014,450:313-322
17 Chen D Y,Wang S J,Xiao M,et al.Preparation and properties of sulfonated poly(fluorenyl ether ketone)membrane for vanadium redox flow battery application.J Power Sources,2010,195:2089-2095
18 Chen L Y,Zhang S H,Chen Y N,et al.Low vanadium ion permeabilities of sulfonated poly(phthalazinone ether ketone)s provide high efficiency and stability for vanadium redox flow batteries.J Power Sources,2017,355:23-30
19 Yun S,Parrondo J,Ramani V.Derivatized cardo-polyetherketone anion exchange membranes for all-vanadium redox flow batteries.JMater Chem A,2014,2:6605-6615
20 Zhang S H,Yin C X,Xing D B,et al.Preparation of chloromethylated/quaternized poly(phthalazinone ether ketone)anion exchange membrane materials for vanadium redox flow battery applications.J Membr Sci,2010,363:243-249
21 Xing D B,Zhang S H,Yin C X,et al.Effect of amination agent on the properties of quaternized poly(phthalazinone ether sulfone)anion exchange membrane for vanadium redox flow battery application.J Membr Sci,2010,354:68-73
22 Zhang B G,Zhang S H,Xing D B,et al.Quaternized poly(phthalazinone ether ketone ketone)anion exchange membrane with low permeability of vanadium ions for vanadium redox flow battery application.J Power Sources,2012,217:296-302
23 Zhang S H,Zhang B G,Zhao G F,et al.Anion exchange membranes from brominated poly(aryl ether ketone)containing 3,5-dimethyl phthalazinone moieties for vanadium redox flow batteries.J Mater Chem A,2014,2:3083-3091
24 Zhang S H,Zhang B G,Jian X G.Preparation and properties of poly(phthalazinone ether ketone)based anion exchange membranes for vanadium redox flow battery.Adv Mater Res,2013,773:171-174
25 Zhang B G,Zhang S H,Xing D B,et al.Quaternized poly(phthalazinone ether ketone ketone)anion-exchange membrane for all-vanadium redox flow battery(in Chinese).Acta Chim Sin,2011,69:2583-2588[张本贵,张守海,邢东博,等.钒电池用季铵化杂萘联苯聚芳醚酮酮阴离子交换膜.化学学报,2011,69:2583-2588]
2 Kear G,Shah A A,Walsh F C.Development of the all-vanadium redox flow battery for energy storage:A review of technological,financial and policy aspects.Int J Energy Res,2012,36:1105-1120
3 Soloveichik G L.Electrochemistry:Metal-free energy storage.Nature,2014,505:163-165
4 Skyllas-Kazacos M,Kazacos G,Poon G,et al.Recent advances with UNSW vanadium-based redox flow batteries.Int J Energy Res,2010,34:182-189
5 Zhang H M,Zhao P,Zhou H T,et al.Vanadium redox flow battery for energy storage(in Chinese).Energy Technol,2005,26:23-26[张华民,赵平,周汉涛,等.钒氧化还原液流储能电池.能源技术,2005,26:23-26]
6 Wen Y H,Zhang H M,Qian P,et al.Study on ion exchange membrane as a separator for all-vanadium redox flow battery(in Chinese).Battery,2005,35:414-416[文越华,张华民,钱鹏,等.离子交换膜全钒液流电池的研究.电池,2005,35:414-416]
7 Ding C,Zhang H M,Li X F,et al.Vanadium flow battery for energy storage:Prospects and challenges.J Phys Chem Lett,2013,4:1281-1294
8 Parasuraman A,Lim T M,Menictas C,et al.Review of material research and development for vanadium redox flow battery applications.Electrochim Acta,2013,101:27-40
9 Li X F,Zhang H M,Mai Z S,et al.Ion exchange membranes for vanadium redox flow battery(VRB)applications.Energy Environ Sci,2011,4:1147-1160
10 Lu W J,Yuan Z Z,Zhao Y Y,et al.Porous membranes in secondary battery technologies.Chem Soc Rev,2017,46:2199-2236
11 Prifti H,Parasuraman A,Winardi S,et al.Membranes for redox flow battery applications.Membranes,2012,2:275-306
12 Yu L H,Lin F,Xu L,et al.A recast Nafion/graphene oxide composite membrane for advanced vanadium redox flow batteries.RSC Adv,2016,6:3756-3763
13 Teng X G,Zhao Y T,Xi J Y,et al.Nafion/organically modified silicate hybrids membrane for vanadium redox flow battery.J Power Sources,2009,189:1240-1246
14 Xi J Y,Wu Z H,Qiu X P,et al.Nafion/SiO2 hybrid membrane for vanadium redox flow battery.J Power Sources,2007,166:531-536
15 Luo Q T,Zhang H M,Chen J,et al.Modification of Nafion membrane using interfacial polymerization for vanadium redox flow battery applications.J Membr Sci,2008,311:98-103
16 Winardi S,Raghu S C,Oo M O,et al.Sulfonated poly(ether ether ketone)-based proton exchange membranes for vanadium redox battery applications.J Membr Sci,2014,450:313-322
17 Chen D Y,Wang S J,Xiao M,et al.Preparation and properties of sulfonated poly(fluorenyl ether ketone)membrane for vanadium redox flow battery application.J Power Sources,2010,195:2089-2095
18 Chen L Y,Zhang S H,Chen Y N,et al.Low vanadium ion permeabilities of sulfonated poly(phthalazinone ether ketone)s provide high efficiency and stability for vanadium redox flow batteries.J Power Sources,2017,355:23-30
19 Yun S,Parrondo J,Ramani V.Derivatized cardo-polyetherketone anion exchange membranes for all-vanadium redox flow batteries.JMater Chem A,2014,2:6605-6615
20 Zhang S H,Yin C X,Xing D B,et al.Preparation of chloromethylated/quaternized poly(phthalazinone ether ketone)anion exchange membrane materials for vanadium redox flow battery applications.J Membr Sci,2010,363:243-249
21 Xing D B,Zhang S H,Yin C X,et al.Effect of amination agent on the properties of quaternized poly(phthalazinone ether sulfone)anion exchange membrane for vanadium redox flow battery application.J Membr Sci,2010,354:68-73
22 Zhang B G,Zhang S H,Xing D B,et al.Quaternized poly(phthalazinone ether ketone ketone)anion exchange membrane with low permeability of vanadium ions for vanadium redox flow battery application.J Power Sources,2012,217:296-302
23 Zhang S H,Zhang B G,Zhao G F,et al.Anion exchange membranes from brominated poly(aryl ether ketone)containing 3,5-dimethyl phthalazinone moieties for vanadium redox flow batteries.J Mater Chem A,2014,2:3083-3091
24 Zhang S H,Zhang B G,Jian X G.Preparation and properties of poly(phthalazinone ether ketone)based anion exchange membranes for vanadium redox flow battery.Adv Mater Res,2013,773:171-174
25 Zhang B G,Zhang S H,Xing D B,et al.Quaternized poly(phthalazinone ether ketone ketone)anion-exchange membrane for all-vanadium redox flow battery(in Chinese).Acta Chim Sin,2011,69:2583-2588[张本贵,张守海,邢东博,等.钒电池用季铵化杂萘联苯聚芳醚酮酮阴离子交换膜.化学学报,2011,69:2583-2588]