Journal of Textile Research ›› 2020, Vol. 41 ›› Issue (06): 8-13.doi: 10.13475/j.fzxb.20190600506

• Fiber Materials • Previous Articles     Next Articles

Preparation and properties of proton exchange membrane made from graphene oxide quantum dots/polyacrylonitrile nanofiber composites

WANG Shubo1,2, QIN Xiangpu3, SHI Lei3, ZHUANG Xupin3(), LI Zhenhuan1,2   

  1. 1. School of Materials Science and Engineering, Tiangong University, Tianjin 300387, China
    2. State Key Laboratory of Separation Membranes and Membrane Processes, Tiangong University,Tianjin 300387, China
    3. School of Textile Science and Engineering, Tiangong University, Tianjin 300387, China
  • Received:2019-06-03 Revised:2020-03-15 Online:2020-06-15 Published:2020-06-28
  • Contact: ZHUANG Xupin E-mail:zhxupin@tjpu.edu.cn

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Abstract:

In order to improve the proton conductivity and dimensional stability of the Nafion proton exchange membrane, a well-designed structure is in high demand. A graphene oxide quantum dot (GOQDs) / polyacrylonitrile (PAN) nanofiber membrane was prepared by electrostatic spinning technology, and a nanofiber composite proton exchange membrane was prepared by Nafion solution impregnation method. The structures and properties of nanofibers and composite membranes were characterized by scanning electron microscope, confocal microscopy, thermal gravimetric analyzer and X-ray diffractometer. The results show that GOQDs are evenly distributed in PAN nanofibers, and the addition of GOQDs reduces the diameter of the nanofiber. The three-dimensional network structure of nanofibers plays a skeletal support role in the composite membrane, which improves the dimensional stability of the composite membrane. At the same time, the thermal stability and water absorption of the composite membrane is improved. With the increase of GOQDs mass fraction, the proton conductivity of the composite membrane is improved, and the maximum proton conductivity of the composite membrane reaches 0.182 S/cm at 80 ℃.

Key words: electrospinning, polyacrylonitrile nanofiber, graphene oxide quantum dot, proton exchange membrane, fuel cell

CLC Number: 

  • TM911.4

Fig.1

Preparation process of PAN-GOQDs/Nafion composite proton exchange membranes"

Fig.2

SEM images of PAN and PAN-GOQDs nanofiber membranes"

Fig.3

SEM images of PAN-GOQDs/Nafion composite proton exchange membranes. (a) Surface of PAN-GOQDs2/Nafion; (b) Cross-section of PAN-GOQDs1/Nafion; (c) Cross-section of PAN-GOQDs2/Nafion; (d) Cross-section of PAN-GOQDs3/Nafion"

Fig.4

CLSM images of nanofibers and composite proton exchange membranes"

Fig.5

TG curves of composite proton exchange membranes"

Fig.6

XRD diffraction patterns of nanofiber membranes and composite proton exchange membranes"

Tab.1

Water absorption and swelling rate of composite proton exchange membranes at different temperatures%"

样品名称 吸水率 溶胀率
20 ℃ 40 ℃ 60 ℃ 80 ℃ 20 ℃ 40 ℃ 60 ℃ 80 ℃
重铸Nafion 13.2 20.5 31.9 42.6 13.6 14.6 17.7 21.1
PAN/Nafion 12.8 18.9 30.2 40.9 8.2 9.5 11.9 15.4
PAN-GOQDs1/Nafion 17.8 24.3 33.6 45.7 8.4 9.7 12.4 16.2
PAN-GOQDs2/Nafion 22.4 30.1 37.8 50.4 9.9 11.2 14.1 17.1
PAN-GOQDs3/Nafion 24.1 32.7 40.6 55.4 10.8 12.3 15.4 18.1

Tab.2

Proton conductivity of composite proton exchange membranes at different temperaturesS·cm-1"

样品名称 20 ℃ 40 ℃ 60 ℃ 80 ℃
重铸Nafion 0.021 0.049 0.084 0.109
PAN/Nafion 0.019 0.045 0.082 0.104
PAN-GOQDs1/Nafion 0.029 0.067 0.108 0.153
PAN-GOQDs2/Nafion 0.043 0.075 0.125 0.171
PAN-GOQDs3/Nafion 0.052 0.078 0.133 0.182

Fig.7

Mechanical performance curves of composite proton exchange membranes"

[1] HAN R, WU P. Composite proton-exchange membrane with highly improved proton conductivity prepared by in situ crystallization of porous organic cage[J]. ACS Applied Materials & Interfaces, 2018,10(21):18351-18358.
pmid: 29745640
[2] BAKANGURA E, WU L, GE L, et al. Mixed matrix proton exchange membranes for fuel cells: state of the art and perspectives[J]. Progress in Polymer Science, 2016,57:103-152.
[3] PEIGHAMBARDOUST S J, ROWSHANZAMIR S, AMJADI M. Review of the proton exchange membranes for fuel cell applications[J]. International Journal of Hydrogen Energy, 2010,35(17):9349-9384.
[4] ALBERTI G, NARDUCCI R, SGANAPPA M. Effects of hydrothermal/thermal treatments on the water-uptake of Nafion membranes and relations with changes of conformation, counter-elastic force and tensile modulus of the matrix[J]. Journal of Power Sources, 2008,178(2):575-583.
[5] ZHANG H, SHEN P K. Recent development of polymer electrolyte membranes for fuel cells[J]. Chemical Reviews, 2012,112(5):2780-2832.
pmid: 22339373
[6] LUO W, ZHAO L. Inorganic-organic hybrid membranes with anhydrous proton conduction prepared from tetraethoxysilane, 3-glycidyloxypropyltrimethoxysilane, trimethyl phosphate and diethylethylammonium trifluoromethanesulfonate[J]. Journal of Membrane Science, 2014,451:32-39.
[7] LI J, WANG S, XU J, et al. Organic-inorganic composite membrane based on sulfonated poly (arylene ether ketone sulfone) with excellent long-term stability for proton exchange membrane fuel cells[J]. Journal of Membrane Science, 2017,529:243-251.
[8] SHEN C, GUO Z, CHEN C, et al. Preparation of inorganic-organic hybrid proton exchange membrane with chemically bound hydroxyethane diphosphonic acid[J]. Journal of Applied Polymer Science, 2012,126(3):954-959.
[9] LEE C, JO S M, CHOI J, et al. SiO2/sulfonated poly ether ether ketone (SPEEK) composite nanofiber mat supported proton exchange membranes for fuel cells[J]. Journal of Materials Science, 2013,48(10):3665-3671.
[10] DIVONA M, AHMED Z, BELLITTO S, et al. SPEEK-TiO2 nanocomposite hybrid proton conductive membranes via in situ mixed sol-gel process[J]. Journal of Membrane Science, 2007,296(1/2):156-161.
[11] JIANG Z, ZHAO X, MANTHIRAM A. Sulfonated poly(ether ether ketone) membranes with sulfonated graphene oxide fillers for direct methanol fuel cells[J]. International Journal of Hydrogen Energy, 2013,38(14):5875-5884.
[12] TSENG C, YE Y, CHENG M, et al. Sulfonated polyimide proton exchange membranes with graphene oxide show improved proton conductivity, methanol crossover impedance, and mechanical properties[J]. Advanced Energy Materials, 2011,1(6):1220-1224.
[13] HE Y, TONG C, GENG L, et al. Enhanced performance of the sulfonated polyimide proton exchange membranes by graphene oxide: size effect of graphene oxide[J]. Journal of Membrane Science, 2014,458:36-46.
[14] KONG B, ZHU A, DING C, et al. Carbon dot-based inorganic-organic nanosystem for two-photon imaging and biosensing of pH variation in living cells and tissues[J]. Advanced Materials, 2012,24(43):5844-5848.
pmid: 22933395
[15] WU W, LI Y, LIU J, et al. Molecular-level hybridization of Nafion with quantum dots for highly enhanced proton conduction[J]. Advanced Materials, 2018,30(16):1707516.
[16] CAO L, MEZIANI M J, SAHU S, et al. Photoluminescence properties of graphene versus other carbon nanomaterials[J]. Accounts of Chemical Research, 2012,46(1):171-180.
pmid: 23092181
[17] XU X, LI R, TANG C, et al. Cellulose nanofiber-embedded sulfonated poly (ether sulfone) membranes for proton exchange membrane fuel cells[J]. Carbohydrate Polymers, 2018,184:299-306.
[18] HASANI-SADRABADI M M, SHABANI I, SOLEIMANI M, et al. Novel nanofiber-based triple-layer proton exchange membranes for fuel cell applications[J]. Journal of Power Sources, 2011,196(10):4599-4603.
[19] YAO Y, JI L, LIN Z, et al. Sulfonated polystyrene fiber network-induced hybrid proton exchange mem-branes[J]. ACS Applied Materials & Interfaces, 2011,3(9):3732-3737.
doi: 10.1021/am2009184 pmid: 21838242
[20] ESCORIHUELA J, GARCÍA-BERNABÉ A, MONTERO A, et al. Proton conductivity through polybenzimidazole composite membranes containing silica nanofiber mats[J]. Polymers, 2019,11(7):1182.
[21] CAI Z, LI R, XU X, et al. Embedding phosphoric acid-doped cellulose nanofibers into sulfonated poly (ether sulfone) for proton exchange membrane[J]. Polymer, 2018,156:179-185.
[22] GAO Q J, WANG Y X, XU L, et al. Proton-exchange sulfonated poly(ether ether ketone)/sulfonated phenolphthalein poly(ether sulfone) blend membranes in DMFCs[J]. Chinese Journal of Chemical Engineering, 2009,17(6):934-941.
[23] YANG H N, LEE W H, CHOI B S, et al. Preparation of Nafion/Pt-containing TiO2/graphene oxide composite membranes for self-humidifying proton exchange membrane fuel cell[J]. Journal of Membrane Science. 2016,504:20-28.
[24] GENIES C, MERCIER R, SILLION B, et al. Soluble sulfonated naphthalenic polyimides as materials for proton exchange membranes[J]. Polymer, 2001,42(2):359-373.
[25] JIN J, HAO R, HE X, et al. Sulfonated poly(phenylsulfone)/fluorinated polybenzoxazole nanofiber composite membranes for proton exchange membrane fuel cells[J]. International Journal of Hydrogen Energy, 2015,40(41):14421-14427.
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