Acid–base core–shell microspheres are incorporated into proton exchange membranes to effectively alleviate the rapid decline in proton conductivity at low humidity
Restricted accessResearch articleFirst published online March, 2021
Acid–base core–shell microspheres are incorporated into proton exchange membranes to effectively alleviate the rapid decline in proton conductivity at low humidity
The development of a proton exchange membrane (PEM) that can avoid rapid decay of proton conductivity under low humidity is of great significance for the practical application of PEMFC. In this study, acid–base core–shell microspheres (PCSMs-MA@TAC) with a carboxylic acid core and a triazine shell were synthesized by distillation-precipitation polymerization using cross-linked carboxylic acid microspheres (PMAA) as seeds. These PCSMs were then incorporated into a sulfonated poly(ether ether ketone) matrix to make hybrid membranes. Incorporation of PCSMs microspheres can not only strengthen the vehicle mechanism by increasing the water uptake of the membrane, but also the acid–base pairs formed at the SPEEK/PCSMs interface provide a new low-energy barrier pathway for proton hopping, thereby enhancing the proton conduction of the Grotthuss mechanism. The results show that when the content is 10 wt%, the proton conductivity of the SPEEK/PCSMs-MA@TAC composite membrane can reach 0.161 S cm−1 at 80°C and 100% RH, which is 19.3% higher than the SPEEK control membrane (0.135 S cm−1). In particular, even at 60% RH, the proton conductivity of the SPEEK/PCSMs-MA@TAC-10 composite membrane is still 67 mS cm−1, which is 3.16 times higher than that of the SPEEK membrane. Therefore, the SPEEK/PCSMs-MA@TAC composite membrane can maintain superior performance even under high temperature and low humidity conditions.
PedersenBPBuch-PedersenMJMorthJ P, et al.Crystal structure of the plasma membrane proton pump. Nature2007; 450: 1111–1114.
2.
ZhangHShenPK. Recent development of polymer electrolyte membranes for fuel cells. Chem Rev2012; 112: 2780–2832.
3.
ShinDWGuiverMDLeeYM.Hydrocarbon-based polymer electrolyte membranes: importance of morphology on ion transport and membrane stability. Chem Rev2017; 117: 4759–4805.
4.
ChandanAHattenbergerMEl-KharoufA, et al.High temperature (HT) polymer electrolyte membrane fuel cells (PEMFC)—a review. J Power Sources2013; 231: 264–278.
5.
DupuisAC.Proton exchange membranes for fuel cells operated at medium temperatures: materials and experimental techniques. Prog Mater Sci2011; 56: 289–327.
6.
GebelG.Structure of membranes for fuel cells: SANS and SAXS analyses of sulfonated PEEK membranes and solutions. Macromolecules2013; 46: 6057–6066.
7.
Laberty-RobertCValleKPereiraF, et al.Design and properties of functional hybrid organic–inorganic membranes for fuel cells. Chem Soc Rev2011; 40: 961–1005.
8.
HicknerMAPivovarBC. The chemical and structural nature of proton exchange membrane fuel cell properties. Fuel Cells2005; 5: 213–229.
9.
KreuerKD.Proton conductivity: materials and applications. Chem Mater1996; 8: 610–641.
WangJTYueXJZhangZZ, et al.Enhancement of proton conduction at low humidity by incorporating imidazole microcapsules into polymer electrolyte membranes. Adv Funct Mater2012; 22: 4539–4546.
12.
LiZYYueXJHeGW, et al.Enhanced water retention and low-humidity proton conductivity of sulfonated poly(ether ether ketone) hybrid membrane by incorporating ellipsoidal microcapsules. Int J Hydrog Energy2015; 40: 8398–8406.
13.
HeGWLiYFLiZY, et al.Enhancing water retention and low-humidity proton conductivity of sulfonated poly(ether ether ketone) composite membrane enabled by the polymer-microcapsules with controllable hydrophilicity–hydrophobicity. J Power Sources2014; 248: 951–961.
14.
ColicchioIWenFKeulH, et al.Sulfonated poly(ether ether ketone)–silica membranes doped with phosphotungstic acid. Morphology and proton conductivity. J Membr Sci2009; 326: 45–57.
15.
CuiXZhongSWangH. Organic–inorganic hybrid proton exchange membranes based on silicon-containing polyacrylate nanoparticles with phosphotungstic acid. J Power Sources2007; 173: 28–35.
16.
PereiraFValléKBellevilleP, et al.Advanced mesostructured hybrid silica−Nafion membranes for high-performance PEM fuel cell. Chem Mater2008; 20: 1710–1718.
17.
GhassemzadehLPaceGDi NotoV, et al.Effect of SiO2 on the dynamics of proton conducting [Nafion/(SiO2)X] composite membranes: a solid-state 19F NMR study. Phys Chem Chem Phys2011; 13: 9327–9334.
18.
WuHCaoYShenX H, et al.Preparation and performance of different amino acids functionalized titania-embedded sulfonated poly (ether ether ketone) hybrid membranes for direct methanol fuel cells. J Membr Sci2014; 463: 134–144.
19.
AzizMAShanmugamS. Zirconium oxide nanotube–Nafion composite as high performance membrane for all vanadium redox flow battery. J Power Sources2017; 337: 36–44.
20.
SonDHSharmaRKShulYG, et al.Preparation of Pt/zeolite–Nafion composite membranes for self-humidifying polymer electrolyte fuel cells. J Power Sources2007; 165: 733–738.
KimYChoiYKimHK, et al.New sulfonic acid moiety grafted on montmorillonite as filler of organic–inorganic composite membrane for non-humidified proton-exchange membrane fuel cells. J Power Sources2010; 195: 4653–4659.
23.
AlbertiGCasciolaMPicaM, et al.New preparation methods for composite membranes for medium temperature fuel cells based on precursor solutions of insoluble inorganic compounds. Fuel Cells2005; 5: 366–374.
24.
WangJTBaiHJZhangHQ, et al.Anhydrous proton exchange membrane of sulfonated poly(ether ether ketone) enabled by polydopamine-modified silica nanoparticles. Electrochim Acta2015; 152: 443–455.
25.
ZhangWZhangBHeGW, et al.Enhanced water retention and proton conductivity of proton exchange membranes by incorporating hollow polymer microspheres grafted with sulfonated polystyrene brushes. RSC Adv2015; 5: 5343–5356.
26.
YangHWuHShenXH, et al.Enhanced proton conductivity of proton exchange membrane at low humidity based on poly(methacrylic acid)-loaded imidazole microcapsules. RSC Adv2015; 5: 9079–9088.
27.
LiYWuHYinYH, et al.Fabrication of Nafion/zwitterion-functionalized covalent organic framework composite membranes with improved proton conductivity. J Membr Sci2018; 568: 1–9.
28.
NieLLWangJTXuT, et al.Enhancing proton conduction under low humidity by incorporating core–shell polymeric phosphonic acid submicrospheres into sulfonated poly(ether ether ketone) membrane. J Power Sources2012; 213: 1–9.
29.
WangJTZhangZZYueXJ, et al.Independent control of water retention and acid–base pairing through double-shelled microcapsules to confer membranes with enhanced proton conduction under low humidity. J Mater Chem A2013; 1: 2267–2277.
30.
HeYKWangJTZhangHQ, et al.Polydopamine-modified graphene oxide nanocomposite membrane for proton exchange membrane fuel cell under anhydrous conditions. J Mater Chem A2014; 2: 9548–9558.
31.
SithambaranathanPNasefMMAhmadA, et al.Crosslinked composite membrane by radiation grafting of 4-vinylpyridine/triallyl-cyanurate mixtures onto poly(ethylene-co-tetrafluoroethylene) and phosphoric acid doping. Int J Hydrog Energy2017; 42: 9333–9341.
32.
YinYHWangHYCaoL, et al.Sulfonated poly(ether ether ketone)-based hybrid membranes containing graphene oxide with acid-base pairs for direct methanol fuel cells. Electrochim Acta2016; 203: 178–188.
33.
WangJTBaiHJZhangJK, et al.Acid-base block copolymer brushes grafted graphene oxide to enhance proton conduction of polymer electrolyte membrane. J Membr Sci2017; 531: 47–58.
34.
ChengTFengMNHuangYM, et al.SGO/SPEN-based highly selective polymer electrolyte membranes for direct methanol fuel cells. Ionics2017; 23: 2143–2152.
35.
ChaiZLWangCZhangHJ, et al.Nafion–carbon nanocomposite membranes prepared using hydrothermal carbonization for proton-exchange-membrane fuel cells. Adv Funct Mater2010; 20: 4394–4399.
36.
HuangYMChengTZhangXC, et al.Novel composite proton exchange membrane with long-range proton transfer channels constructed by synergistic effect between acid and base functionalized graphene oxide. Polymer2018; 149: 305–315.
37.
WangJTJiangSAZhangH, et al.Enhancing proton conduction and methanol barrier performance of sulfonated poly(ether ether ketone) membrane by incorporated polymer carboxylic acid spheres. J Membr Sci2010; 364: 253–262.
38.
MayahiAIsmailAFIlbeygiH, et al.Effect of operating temperature on the behavior of promising SPEEK/cSMM electrolyte membrane for DMFCs. Sep Purif Technol2013; 106: 72–81.
39.
HuFQLiTZhongF, et al.Preparation and properties of chitosan/acidified attapulgite composite proton exchange membranes for fuel cell applications. J Appl Polym Sci2020; 137: 49079.
40.
ZhaoQWeiYCNiCJ, et al.Property improvement of nanocellulose-reinforced proton exchange nanocomposite membrane coated with tetraethyl orthosilicate. J Polym Sci Polym Chem2019; 57: 2190–2200.
41.
WangJGongCLWenS, et al.A facile approach of fabricating proton exchange membranes by incorporating polydopamine-functionalized carbon nanotubes into chitosan. Int J Hydrog Energy2019; 44: 6909–6918.
42.
FengMNYouYZhengPL, et al.Low-swelling proton-conducting multi-layer composite membranes containing polyarylene ether nitrile and sulfonated carbon nanotubes for fuel cells. Int J Hydrog Energy2016; 41: 5113–5122.
43.
WangJTZhangHYangXL, et al.Enhanced water retention by using polymeric microcapsules to confer high proton conductivity on membranes at low humidity. Adv Funct Mater2011; 21: 971–978.
44.
BanoSNegiYSIllathvalappilR, et al.Studies on nano composites of SPEEK/ethylene glycol/cellulose nanocrystals as promising proton exchange membranes. Electrochim Acta2019; 293: 260–272.
45.
LeeWHLeeKHShinDW, et al.Dually cross-linked polymer electrolyte membranes for direct methanol fuel cells. J Power Sources2015; 282: 211–222.
46.
ParkMJDowningKHJacksonA, et al.Increased water retention in polymer electrolyte membranes at elevated temperatures assisted by capillary condensation. Nano Lett2007; 7: 3547–3552.
TricoliVOrsiniGAnselmiM. Ion transport in a class of imidazole-based liquid/solid protic ionics. Phys Chem Chem Phys2012; 14: 10979–10986.
49.
XuQBWangLLiC, et al.Study on improvement of the proton conductivity and anti-fouling of proton exchange membrane by doping SGO@SiO2 in microbial fuel cell applications. Int J Hydrog Energy2019; 44: 15322–15332.
50.
ParkJKimD. Sulfonated mesoporous benzene-silica-embedded sulfonated poly(ether ether ketone) membranes for enhanced proton conduction and anti-dehydration. Int J Hydrog Energy2014; 39: 1063–1070.
