干法制备燃料电池用模压膨胀石墨/树脂复合板的性能
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摘要
选用膨胀石墨(EG)为导电填料,树脂为粘结料,采用干法混合及模压成型工艺制备复合板;该工艺保持了石墨蠕虫原有的三维网状结构,使其在具备良好导电导热性的同时还有良好的柔韧性、气密性及机械强度。考察了不同含量的聚酰亚胺(PI)、苯并恶嗪(BZ)、酚醛树脂(PF)和聚偏氟乙烯(PVDF)所制备的复合板的电导率、气密性和抗弯强度等重要指标。结果表明,当PI、BZ和PVDF含量为30%或40%(质量分数)时,所制得的复合板的电导率最小值为136.6S·cm-1,氢气渗透率最大值为1.938×10-6 cm3·cm-2·s-1,抗弯强度最小值为58.8MPa,各指标均满足DOE的要求。
Expanded graphite was selected as conductive filler and resins as matrices.The expanded graphite and a resin were first dry mixed and then compression molded.This processing approach allowed the graphite worms to keep three-dimensional network structures,and thus leading to the composite plate having not only good electrical and thermal conductivity,but also excellent flexibility,gas permeability and mechanical strength.Four resins,polyimide(PI),polybenzoxazine(BZ),phenolic resin(PF)and polyvinylidene fluoride(PVDF),were evaluated and for each resin its weight ratio to expanded graphite was also examined.The prepared composite samples were tested in electrical conductivity,gas permeability and flexural strength.The results showed that when the content of PI,BZ or PVDF was 30wt%or 40wt%,the lowest electrical conductivity is 136.6S·cm-1,the highest gas permeability is1.938×10-6 cm3·cm-2·s-1 and the minimum flexural strength is 58.8 MPa among all of the composite plates,therefore all of them can meet the DOE targets.
Expanded graphite was selected as conductive filler and resins as matrices.The expanded graphite and a resin were first dry mixed and then compression molded.This processing approach allowed the graphite worms to keep three-dimensional network structures,and thus leading to the composite plate having not only good electrical and thermal conductivity,but also excellent flexibility,gas permeability and mechanical strength.Four resins,polyimide(PI),polybenzoxazine(BZ),phenolic resin(PF)and polyvinylidene fluoride(PVDF),were evaluated and for each resin its weight ratio to expanded graphite was also examined.The prepared composite samples were tested in electrical conductivity,gas permeability and flexural strength.The results showed that when the content of PI,BZ or PVDF was 30wt%or 40wt%,the lowest electrical conductivity is 136.6S·cm-1,the highest gas permeability is1.938×10-6 cm3·cm-2·s-1 and the minimum flexural strength is 58.8 MPa among all of the composite plates,therefore all of them can meet the DOE targets.
引文
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18 王臣.新型石墨基复合双极板的研制[D].上海:华东理工大学,2013
19 陈惠,刘洪波,涂文懋,等.膨胀石墨/酚醛树脂复合材料双极板研究[J].中南大学学报:自然科学版,2011,42(11):3326
20 竺斌.聚偏氟乙烯、高铝水泥/填料复合材料双极板的制备与性能研究[D].武汉:武汉理工大学,2008
21 Graftech.Technical Bulletin 2011.http://www.graftechaet.com/GRAFCELL/GRAFCELL Technical-Documents.aspx
22 In Uk Hwang,Ha Na Yu,Seong Su Kim,et al.Bipolar plate made of carbon fiber epoxy composite for polymer electrolyte membrane fuel cells[J].J Power Sources,2008,184:90
23 Oong Hee Lee,Yun Ki Jang,Chang Eui Hong,et al.Effect of carbon fillers on properties of polymer composite bipolar plates of fuel cells[J].J Power Sources,2009,193:523
24 Renato A Antunes,et al.Carbon materials in composite bipolar plates for polymer electrolyte membrane fuel cells:A review of the main challenges to improve electrical performance[J].J Power Sources,2011,196:2945
25 刘昱.环氧树脂/石墨复合材料双极板的制备研究[D].武汉:武汉理工大学,2012
2 Larriba T,Garde R,Santarelli M.Fuel cell early markets:Techno-economic feasibility study of PEMFC-based drivetrains in materials handling vehicles[J].Int J Hydrogen Energy,2013,38(5):2009
3 Vladimir S Bagotsky.燃料电池——问题与对策[M].北京:人民邮电出版社,2011
4 Antunes Renato A,et al.Carbon materials in composite bipolar plates for polymer electrolyte membrane fuel cells:A review of the main challenges to improve electrical performance[J].J Power Sources,2011,196(6):2945
5 侯明,俞红梅,衣宝廉.车用燃料电池技术的现状与研究热点[J].化学进展,2009,21(11):2319
6 Dhakate S R,Sharma S,Borah M,et al.Expanded graphitebased electrically conductive composites as bipolar plate for PEM fuel cell[J].Int J Hydrogen Energy,2008,33(23):7146
7 Brent D Cunningham,Huang Jianhua,Donald G Baird.Development of bipolar plates for fuel cells from graphite filled wet-lay material and a thermoplastic laminate skin layer[J].J Power Sources,2007,165(2):764
8 张华勇.石墨导电复合材料制备及性能研究[D].济南:山东大学,2006
9 刘宗浩.用于PEMFC的石墨/聚合物复合材料双极板研究[D].天津:天津大学,2005
10 马小杰.质子交换膜燃料电池用石墨复合板的研究[D].杭州:浙江大学,2006
11 罗晓宽,侯明,傅云峰,等.质子交换膜燃料电池模压石墨双极板研究[J].电源技术,2008,32(3):174
12 Oswin Ottinger,Jurgen Bacher.Acrylic resin-impregnated bodies formed of expanded graphite,process for producing such bodies and sealing elements,fuel cell components and heat-conducting elements formed of the bodies:US2002/0127390A1[P].2002-12-09
13 Huang Jianhua,Donald G Baird,James E McGrath.Development of fuel cell bipolar plates from graphite filled wetlay thermoplastic composite materials[J].J Power Sources,2005,150:110
14 Daniel J L Brett,Nigel P Brandon.Review of materials and characterization methods for polymer electrolyte fuel cell flow-field plates[J].Fuel Cell Sci Techn,2007,4:29
15 李建新,刘洪波,陈惠.超声分散技术在燃料电池复合材料双极板制备中的应用[J].碳素技术,2010,29(4):9
16 Allahbakhsh Ahmad,Sheydaei Milad,Mazinani Saeedeh.Enhanced thermal properties of poly(ethylene tetrasulfide)via expanded graphite incorporation by in situ polymerization method[J].High Performance Polymers,2013,25(5):576
17Cui Tongmin,Li Ping,Liu Yi,et al.Preparation of thermostable electroconductive composite plates from expanded graphite and polyimide[J].Mater Chem Phys,2012,134(23):1160
18 王臣.新型石墨基复合双极板的研制[D].上海:华东理工大学,2013
19 陈惠,刘洪波,涂文懋,等.膨胀石墨/酚醛树脂复合材料双极板研究[J].中南大学学报:自然科学版,2011,42(11):3326
20 竺斌.聚偏氟乙烯、高铝水泥/填料复合材料双极板的制备与性能研究[D].武汉:武汉理工大学,2008
21 Graftech.Technical Bulletin 2011.http://www.graftechaet.com/GRAFCELL/GRAFCELL Technical-Documents.aspx
22 In Uk Hwang,Ha Na Yu,Seong Su Kim,et al.Bipolar plate made of carbon fiber epoxy composite for polymer electrolyte membrane fuel cells[J].J Power Sources,2008,184:90
23 Oong Hee Lee,Yun Ki Jang,Chang Eui Hong,et al.Effect of carbon fillers on properties of polymer composite bipolar plates of fuel cells[J].J Power Sources,2009,193:523
24 Renato A Antunes,et al.Carbon materials in composite bipolar plates for polymer electrolyte membrane fuel cells:A review of the main challenges to improve electrical performance[J].J Power Sources,2011,196:2945
25 刘昱.环氧树脂/石墨复合材料双极板的制备研究[D].武汉:武汉理工大学,2012