Synthesis and Properties of Sulfonated Polyether Ketone/Barium Titanate Proton Exchange Membrane
WNAG Wenjuan, CHEN Pei, AN Zhongwei, CHEN Xinbing*
Key Laboratory of Applied Surface and Colloid Chemistry of Ministry of Education, School of Materials Science and Engineering,Shaanxi Normal University,Xi'an 710119,China
Fund:Supported by the National Natural Science Foundation of China(No.51373092 ), the Key Science and Technology Program of Shaanxi Province, China(No.2012K08-09), the State Education Ministry and the Fundamental Research Funds for the Central Universities(No.GK201302036, No.GK201302037)
Abstract
To prepare sulfonated polyether ketone/barium titanate(SPAEK/BT) hybrid membrane, the mixture containing BT suspension in cyclohexane obtained under ultrasonic condition and dimethyl sulfoxide solution of SPAEK was casted onto the glass plates. The uniform dispersion of BT in the hybrid membrane was confirmed via SEM. The properties of the corresponding hybrid membranes, such as water uptake, solvent uptake, size change, proton conductivity, methanol permeability, mechanical properties, and stabilities were investigated. Compared to blank membrane, the anti-swelling, thermal stability, and oxidative stability of hybrid membranes are improved respectively. The water stability and mechanical properties are also improved, whereas the proton conductivity of the hybrid membrane is decreased in some extent.
a.Ca or Titr: calculated or titrated IEC value; b.SU was obtained at 32% mass fraction of methanol solution and 25 ℃; SU/%=100(mmw-md)/md; mmw or md:the mass of the swollen or dry membranes; c.WU/%=100(mS-md)/md; in water; ms:the mass of the swollen membranes; d.Δ tc=(ts-td)/td; Δ lc=(ls-ld)/ld; Δ t/l=Δ tc/Δ lc; td and ld:the thickness and length of the dry membrane, respectively; ts and ls refer to those of the membrane immersed in water; e.R1:30%BT & R; R2:40%BT & R.
表2 膜的电导率、抗氧化性、甲醇吸收率、力学性能和水稳定性数据Table 2 Proton conductivity, oxidative stability, methanol uptake, methanol permeability, mechanical property and water stability of membranes
Membrane
σ a/(mS· m-1)
/min
MUc/%
107/(cm2· s-1)
Mechanical property
Water stabilityh
25 ℃
85 ℃
YMe/GPa
MSf/MPa
EBg/%
Mass loss/%
SPAEK
84.86
184.10
137
21.67
0.59
1.24
31.06
25.04
18.37
SPAEK-BT30
43.90
128.77
260
S
1.95
3.81
41.86
11.00
12.37
SPAEK-BT40
35.65
112.85
312
S
2.33
2.76
47.11
17.04
11.29
R1
26.60
65.31
251
22.82
2.40
3.32
56.84
17.10
5.71
R2
24.84
53.14
271
26.49
2.59
1.65
82.67
50.00
5.62
a. σ :proton conductivity in water; b.τ 1:oxidative stability, refers to the elapsed time that the membranes became broken; c.MU:methanol uptake; at 25 ℃; d.PM:methanol permeability; at 32wt.% methanol solution and 25 ℃; e.YM:Young's modulus; f.MS:maximum stress; g.EB:elongation at break; h.aging in sealed autoclave in water at 130 ℃ for 48 h.
表2 膜的电导率、抗氧化性、甲醇吸收率、力学性能和水稳定性数据Table 2 Proton conductivity, oxidative stability, methanol uptake, methanol permeability, mechanical property and water stability of membranes
ZhangH, Shen PK. Recent Development of Polymer Electrolyte Membranes for Fuel Cells[J]. Chem Rev, 2012, 112: 2780-2832. [本文引用:1][JCR: 41.298]
[2]
HigashiharaT, MatsumotoK, UedaM. Sulfonated Aromatic Hydrocarbon Polymers as Proton Exchange Membranes for Fuel Cells[J]. Polymer, 2009, 50: 5341-5357. [本文引用:1][JCR: 3.379]
[3]
GuoM, LiuB, GuanS, et al. Novel Sulfonated Poly(ether ether ketone)s Containing Nitrile Groups and Their Composite Membranes for Fuel Cells[J]. J Power Sources, 2010, 195: 4613-4621. [本文引用:1][JCR: 4.675]
Jalani NH, DunnK, DattaR. Synthesis and Characterization of Nafion-MO2(M=Zr, Si, Ti) Nanocomposite Membranes for Higher Temperature PEM Fuel Cells[J]. Electrochim Acta, 2005, 51(3): 553-560. [本文引用:1][JCR: 3.777]
[7]
LiK, Ye GB, Pan JJ, et al. Self-assembled Nafion/metal Oxide Nanoparticles Hybrid Proton Exchange Membranes[J]. J Membr Sci, 2010, 347: 26-31. [本文引用:1]
[8]
QIANJiasheng, CHENXiaoming, HEPingsheng. Preparation and Characterization of PMMA/nano-SiO2 Nanocomposite[J]. Chinese J Appl Chem, 2003, 20(12): 1200-1203(in Chinese). 钱家盛, 陈晓明, 何平笙. PMMA/nano-SiO2纳米复合材料的制备和表征[J]. 应用化学, 2003, 20(12): 1200-1203. [本文引用:1][CJCR: 0.741]
[9]
Lim YD, Jang HY, Jeon YT, et al. Nano Composite Membranes of Poly(ether sulfone)s Containing Multi-sulfonated Hexaphenylbenzene and SiO2 for PEMFC[J]. Adv Mater Res, 2013, 746: 78-82. [本文引用:1]
[10]
HooshyariK, JavanbakhtM, NajiL, et al. Nanocomposite Proton Exchange Membranes Based on Nafion Containing Fe2TiO5 Nanoparticles in Water and Alcohol Environments for PEMFC[J]. J Membr Sci, 2014, 454: 74-81. [本文引用:1]
ChenX, ChenK, ChenP, et al. Effects of Tetracarboxylic Dianhydrides on the Properties of Sulfonated Polyimides[J]. J Polym Sci, Part A: Polym Chem, 2010, 48: 905-915. [本文引用:1][JCR: 3.543]
[13]
ZhangH, WangX, TianZ, et al. Fabrication of Mondispersed 5-nm BaTiO3 Nanocrystals with Narrow Size Distribution via One-Step Solvothermal Route[J]. J Am Ceram Soc, 2011, 94(10): 3220-3222. [本文引用:1][JCR: 2.107]
[14]
ChenX, ChenP, AnZ, et al. Crosslinked Sulfonated Poly(arylene ether ketone) Mmembranes Bearing Quinoxaline and Acid-base Complex Cross-linkages for Fuel Cell Applications[J]. J Power Sources, 2011, 196: 1694-1703. [本文引用:1][JCR: 4.675]
State Key Laboratory of Optoelectronic Materials and Technologies and Key Laboratory of Low-Carbon Chemistry & Energy Conservation of Guangdong Province, School of Physics and Engineering, Sun Yat-sen University, Guangzhou 510275, P.R. China *Phone (office): +86-20-84036736 . Fax: +86-20-84113369 . E-mail: stsspk@mail.sysu.edu.cn .
HigashiharaT, MatsumotoK, UedaM. Sulfonated Aromatic Hydrocarbon Polymers as Proton Exchange Membranes for Fuel Cells[J]. Polymer, 2009, 50: 5341-5357.
Abstract This article reviews recent studies on proton exchange membrane (PEM) materials for polymer electrolyte fuel cells. In particular, it focuses on the development of novel sulfonated aromatic hydrocarbon polymers for PEMs as alternatives to conventional perfluorinated polymers. It is necessary to improve proton conductivity especially under low-humidity conditions at high operating temperatures to breakthrough the current aromatic PEM system. Capable strategies involve the formation of well-connected proton channels by microphase separation between hydrophilic and hydrophobic domains and the increase of the ion exchange capacity of PEMs while keeping water resistance. Herein, we introduce novel molecular designs of sulfonated aromatic hydrocarbon polymers and their performance as PEMs. Graphical abstract
GuoM, LiuB, GuanS, et al. Novel Sulfonated Poly(ether ether ketone)s Containing Nitrile Groups and Their Composite Membranes for Fuel Cells[J]. J Power Sources, 2010, 195: 4613-4621.
HooshyariK, JavanbakhtM, NajiL, et al. Nanocomposite Proton Exchange Membranes Based on Nafion Containing Fe2TiO5 Nanoparticles in Water and Alcohol Environments for PEMFC[J]. J Membr Sci, 2014, 454: 74-81.
The present paper focuses on improving the water-holding ability of sulfonated poly(ether ether ketone) (SPEEK) (degree of sulfonation,DS = 55.1%) membranes.Functionalized silica (silica sol (SiO 2 ) and silica powder with sulfonic acid groups (SiO x -S)) were chosen as the hygroscopic additive,respectively.SPEEK/SiO 2 、SPEEK/SiO x -S composite membranes were obtained by casting a homogeneous mixture of SiO 2 (or SiO x -S) and SPEEK in N,N -dimethylacetamide onto glass plate and then evaporating the solvent at 60℃.The decrease in both the swelling degree and the methanol permeability and the improvement in the conductivity at a high temperature and a low humidity of the membranes were a dose-dependent result of addition of the SiO 2 and SiO x -S powders.Pure SPEEK membranes swelled 52.6% at 80℃,whereas the SPEEK/SiO 2 (15 wt%) and SPEEK/SiO x -S (15 wt%) membranes swelled only 26.2% and 27.3% at the same temperature,respectively.From room temperature to 80℃,SPEEK/SiO 2 (20 wt%) and SPEEK/SiO x -S (20 wt%) membranes had methanol permeability of about two order of magnitude lower than that of Nafion ® 115.At 120℃ and 40% relative humidity (RH),the conductivity of pure SPEEK membranes is only 2.6×10 -4 S·cm -1 ,and that of SPEEK/SiO 2 (20 wt%) membranes is about 2.0×10 -3 S·cm -1 ,while that of SPEEK/SiO x -S (20 wt%) composite membranes reaches 1.0×10 -2 S·cm -1 ,which is close to that of Nafion ® 115.DMFCs single cell performance of SPEEK/SiO 2 (20 wt%) and SPEEK/SiO x -S (20 wt%) membranes was better than that of pure SPEEK membranes because they had good dimensional stability and no separation of catalyzers and membranes in membrane electrode assembles.
1. Institute of Biological and Chemical Engineering, Tianjin 300160; 2. State Key Laboratory of Hollow Fiber Membrane Materials and Processes, Tianjin Polytechnic University, Tianjin 300160; 3. School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072
在磺化度(DS)为55.1%的磺化聚醚醚酮(SPEEK)中掺杂功能化二氧化硅(吸湿性SiO 2 溶胶及带有磺酸基团的二氧化硅(SiO x -S)粒子)制备SPEEK/SiO 2 和SPEEK/SiO x -S复合质子交换膜.SiO 2 和SiO x -S的掺杂能有效提高复合膜的抗溶胀、阻醇性能及高温低湿情况下的电导率.纯SPEEK膜在80℃溶胀为52.6%,而SiO 2 和SiO x -S掺杂量为15%的复合膜在此温度下分别仅有26.2%和27.3%的溶胀.在室温至80℃范围内,SPEEK/SiO 2 (20 wt%)和SPEEK/SiO x -S(20 wt%)复合膜的甲醇透过系数比Nafion ® 115膜小近2个数量级.在120℃、相对湿度(RH)为40%情况下,SPEEK纯膜的电导率仅为2.6×10 -4 S·cm -1 ,SPEEK/SiO 2 (20 wt%)复合膜约为2.0×10 -3 S·cm -1 ,而SPEEK/SiO x -S(20 wt%)复合膜高达1.0×10 -2 S·cm -1 ,与Nafion ® 115相当.SPEEK/SiO 2 (20 wt%)和SPEEK/SiO x -S(20 wt%) 2种复合膜的尺寸稳定性较高,膜电极无催化剂与膜分离现象,其DMFCs单电池性能好于SPEEK膜.
ZhangH, WangX, TianZ, et al. Fabrication of Mondispersed 5-nm BaTiO3 Nanocrystals with Narrow Size Distribution via One-Step Solvothermal Route[J]. J Am Ceram Soc, 2011, 94(10): 3220-3222.
State Key Laboratory of New Ceramics and Fine Processing, Department of Materials Science and Engineering, Tsinghua University, Beijing, China * Author to whom correspondence should be addressed. e-mail: wxh@mail.tsinghua.edu.cn
> A convenient one-step solvothermal route has been developed to synthesize monodispersed barium titanate with narrow size distributions. The key point of this method is the controlling of hydrolysis of Ti(OC 4 H 9 ) 4 with Diethylene glycol. The as-prepared BaTiO 3 nanoparticles were characterized by X-ray diffraction, transmission electron microscopy (TEM), high-resolution TEM, BET-specific surface area measurement and Raman spectrum. The monodispersed BaTiO 3 nanoparticles obtained by this method have an average size of 5 nm with a narrow size distribution and a lattice tetragonality of 1.0069 ± 0.0010, which is promising for the ferroelectric science and its industry application.
1
2011
4.675
0.0
ChenX, ChenP, AnZ, et al. Crosslinked Sulfonated Poly(arylene ether ketone) Mmembranes Bearing Quinoxaline and Acid-base Complex Cross-linkages for Fuel Cell Applications[J]. J Power Sources, 2011, 196: 1694-1703.
Figure1
表1(Table 1)
]
