CN107346829B - Proton exchange membrane and synthesis method and application thereof - Google Patents

Proton exchange membrane and synthesis method and application thereof Download PDF

Info

Publication number
CN107346829B
CN107346829B CN201610297297.1A CN201610297297A CN107346829B CN 107346829 B CN107346829 B CN 107346829B CN 201610297297 A CN201610297297 A CN 201610297297A CN 107346829 B CN107346829 B CN 107346829B
Authority
CN
China
Prior art keywords
exchange membrane
proton
proton exchange
short side
long
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201610297297.1A
Other languages
Chinese (zh)
Other versions
CN107346829A (en
Inventor
程寒松
张运丰
高小平
李然
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Intergrated Power Technology Co ltd
Original Assignee
Intergrated Power Technology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Intergrated Power Technology Co ltd filed Critical Intergrated Power Technology Co ltd
Priority to CN201610297297.1A priority Critical patent/CN107346829B/en
Publication of CN107346829A publication Critical patent/CN107346829A/en
Application granted granted Critical
Publication of CN107346829B publication Critical patent/CN107346829B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/103—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/1023—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon, e.g. polyarylenes, polystyrenes or polybutadiene-styrenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/1025—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon and oxygen, e.g. polyethers, sulfonated polyetheretherketones [S-PEEK], sulfonated polysaccharides, sulfonated celluloses or sulfonated polyesters
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/1027—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having carbon, oxygen and other atoms, e.g. sulfonated polyethersulfones [S-PES]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. insitu polymerisation or insitu crosslinking
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Landscapes

  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Fuel Cell (AREA)
  • Conductive Materials (AREA)

Abstract

The invention discloses a novel proton exchange membrane which is used for suspending acid radical ions containing protonic acid on long/short side chains. The structural design has the advantages that the proton acid suspended on the long/short side chain exists in the proton exchange membrane at the same time, and the distribution area of the proton in the proton exchange membrane is enlarged. Acid radical ions containing protonic acid can increase proton transfer channels after absorbing water molecules. The invention has the advantages that through the design of the structure, the continuous and smooth proton transfer channel in the proton exchange membrane can be better established, which is beneficial to improving the proton conductivity, and the energy density and the energy conversion efficiency of the fuel cell can be greatly improved when the proton exchange membrane is used for the fuel cell.

Description

Proton exchange membrane and synthesis method and application thereof
Technical Field
The invention relates to a proton exchange membrane material for a fuel cell, in particular to a structural design and a concrete implementation example of a proton exchange membrane which can simultaneously suspend acid radical ions containing protonic acid on long and short side chains.
Background
Developing new materials (e.g., catalysts and Exchange membranes) and designing new device models are significant challenges facing the development of Proton Exchange Membrane Fuel Cells (PEMFCs). Proton Exchange Membranes (PEM) are one of the most critical components of a proton exchange membrane fuel cell, requiring high proton conductivity, adequate water absorption, while having a moderate swelling ratio. Perfluorosulfonic acid proton exchange membranes, e.g.
Figure GDA0002472518120000011
Can satisfy the above requirements, but
Figure GDA0002472518120000012
The method has the defects of low proton conductivity under low humidity, electro-osmosis of water, high fuel permeation rate, high cost caused by a perfluorinated framework, environmental friendliness and the like. Therefore, non-fluorosulfonic acid ionomer membrane replacement was developed
Figure GDA0002472518120000013
Is a current research hotspot. But not fluorosulfonic acidsThe membrane has a problem of low proton conductivity at the same Ion Exchange Capacity (IEC). One effective way to increase proton conductivity is to increase the amount of protonic acid (IEC value) in the proton exchange membrane, but a high IEC causes excessive water absorption and severe swelling, even with the problem of dissolution of the membrane at high temperatures.
In order to identify the conduction mechanism of proton in the proton exchange membrane, people put forward several theoretical model simulations according to experimental results
Figure GDA0002472518120000014
The micro-topography of the proton channels, e.g., cluster-network model, short rod model, and lamellar model, these models, etc. According to
Figure GDA0002472518120000015
The research of the micro morphology finds that the connectivity of the water clusters and the distribution of hydrophilic sites are important to the proton conductivity, so that the establishment of a highly effective proton transfer channel by controlling the connectivity of the water clusters and the distribution of the hydrophilic sites is the key to obtain the novel proton exchange membrane with high proton conductivity. Pan et al establishes a high-speed-OH transfer channel with a medium IEC value of 1.0 mmol-g by designing the structure of the ion cluster of the alkaline exchange membrane-1The conductivity of the polymer film reaches 0.1S cm at the temperature of 80 DEG C-1. In previous work, we designed and synthesized a series of rigid-flexible hybrid membrane-exchange membranes, all of which had excellent proton channels, in which the flexible backbone increased the size of the water clusters in the PEM by adding "bulk water" (bulk water is water located in the center of the water clusters, which transported protons at a higher rate than "surface water").
Disclosure of Invention
The invention aims to solve the technical problem that a proton transfer channel in a proton exchange membrane is effectively established through the design of a molecular structure so as to improve the proton conductivity of the proton exchange membrane. The invention provides a channel for increasing proton transfer by simultaneously introducing long/short side chains of suspended proton acid into a proton exchange membrane, and the structural schematic diagram of the channel is shown in figure 1. According to
Figure GDA0002472518120000021
The sandwich proton conduction model (shown in FIG. 1 a) in-SO3H layers (shells) form a width of
Figure GDA0002472518120000022
The proton channel (core). The conductivity of the PEM is primarily determined by "bulk water," which can affect the size of the proton transfer channel. Based on this, we designed to graft hydrophilic groups of different lengths alternately on the backbone to increase the "bulk water" content and proton conduction efficiency, as shown in FIG. 1 b. The long/short side chain crosspolymer has a wider proton transport channel than a PEM containing only long side chains (fig. 1c) or short side chains (fig. 1 d).
Drawings
FIG. 1: schematic drawing of hanging long/short side chain of proton acid to proton exchange membrane: (a)
Figure GDA0002472518120000031
a sandwich structure proton conduction model schematic diagram of the structure, (b) a wide proton channel formed by long/short side chains, (c) a narrow proton channel formed by short side chains, (d) a narrow proton channel formed by long side chains, and (e) a specific implementation example of a long/short side chain proton exchange membrane molecular structure.
FIG. 2: examples of (a) Infrared Spectroscopy and (b) proton exchange membranes1H NMR spectrum.
FIG. 3: TGA curves of the proton exchange membranes of the examples were carried out.
FIG. 4: examples of proton exchange membranes and
Figure GDA0002472518120000032
117 tensile strength and elongation.
FIG. 5: examples of proton exchange membranes and
Figure GDA0002472518120000033
water absorption and swelling ratio of 117.
FIG. 6: examples the proton conductivity of the proton exchange membrane.
Detailed Description
The present invention will be described below in detail with reference to specific embodiments, but is not limited thereto.
The invention provides an application example of a proton exchange membrane scheme which simultaneously suspends acid radical ions containing protonic acid on long/short side chains and takes polyamide resin as a polymer skeleton. In order to present the benefits of the invention, a proton exchange membrane with acid radical ions of protonic acid respectively suspended on long side chains and short side chains is designed and synthesized at the same time, and the molecular structural formula of the proton exchange membrane is shown as follows. By means of FTIR, the measurement of,1HNMR and TGA characterize their structural and thermal properties, providing properties of mechanical strength, water absorption, volume expansion, and proton conductivity. The result shows that the proton exchange membrane which suspends acid radical ions containing protonic acid on long and short side chains has high water absorption capacity ('bulk water') and larger volume expansion (proton transmission channel expansion) at the same time under the same IEC value, and shows that the proton exchange membrane has wider proton transmission channels. Meanwhile, the swelling of the proton exchange membrane suspending acid radical ions containing protonic acid on long/short side chains is lower, and the swelling is shown to be higher than that of a commercial proton exchange membrane
Figure GDA0002472518120000034
117 better dimensional and mechanical stability, proton conductivity close to 10-1S cm-1Far higher than the long side chain proton exchange membrane and the short side chain proton exchange membrane.
Figure GDA0002472518120000041
Molecular structure of proton exchange membrane in implementation application
Figure GDA0002472518120000042
Molecular structure of short side chain for comparison in practical application and long/short side chain proton exchange membrane in practical application
The material used in the embodiments provided in the present invention includes benzene sulfonic acidAmide (Sigma-Aldrich), p-toluenesulfonylchloride (p-methylbenzenesulfonyl chloride) (Sigma-Aldrich), dimethyl 5-aminoisophthalate (5-dimethyl-aminoisophthalate) (Sigma-Aldrich), potassium permanganate (GCE), lithium hydroxide monohydrate (Alfa-Aesar), triphenyl phosphite (TPP) (Alfa-Aesar), and sodium chloride (Alfa-Aesar). 4, 4' - (9-fluororylidene) dianiline (9, 9-bis (4-aminophenyl) Fluorene) (FIDA) (Sigma-Aldrich), sebacic acid (DDA) (Sigma-Aldrich), 2, 4-diaminobenzinesulfonic acid (2, 4-diaminobenzenesulfonic acid) (DBSA) (Sigma-Aldrich), calcium chloride (GCE) and lithium chloride (Sigma-Aldrich) were used after vacuum drying at 100 ℃ for 24 hours. Pyridine was dried over KOH. N-methyl-2-pyrrolidone (NMP) with P2O5And CaCl2Dried, vacuum dried at 180 ℃ for 24h deuterium Dimethylsulfoxide (DMSO) (Cambridge Isotope L laboratories) was used for NMR characterization.
In the specific embodiment of the present invention, the proton exchange membrane synthesis step is shown in FIG. 4, and the specific operation process is that a certain amount of mixture of FIDA, DDA, DBSA, BPSIIA, TPP and L iCl is added into NMP and pyridine, and reacted for 12h at 100 ℃ under nitrogen atmosphere, then the mixture is cooled to 70 ℃ and transferred to cold methanol to be stirred, so as to obtain white solid polymer precipitate, the white precipitate is filtered, washed repeatedly with methanol and water, and finally dried in vacuum for 24h at 140 ℃ and the mass average molecular weight (Mw) is in the range of 235000-309000g/mol, the polydispersity index is close to 1 (Table) and the elemental analysis result of the polymer is matched with the theoretical value (Table 2), thus indicating that the designed polymer is successfully synthesized.
Figure GDA0002472518120000051
When m-n-0.132, the ion exchange capacity IEC is 0.49, and it is labeled as long/short side chain proton exchange membrane-0.49
When m is 0.180, the ion exchange capacity IEC is 0.67, and it is marked as long/short side chain proton exchange membrane-0.67
When m is 0 and n is 0.30, the ion exchange capacity IEC is 0.49, and the label is long side chain proton exchange membrane-0.49
When m is 0.236 and n is 0, the ion exchange capacity IEC is 0.49, and the label is short side chain proton exchange membrane-0.49
The proton exchange membrane synthesis step in the embodiment
TABLE 1 molecular weight of Polymer electrolyte
Figure GDA0002472518120000052
aTesting at room temperature with DMF as solvent and polystyrene as standard substance
TABLE 2 elemental analysis of Polymer electrolytes
Figure GDA0002472518120000061
The preparation process of the proton exchange membrane in the embodiment provided by the invention is to prepare the proton exchange membrane by adopting a solution casting method, and dimethyl sulfoxide (DMSO) is used as a solvent. 0.25g of polymer electrolyte was dissolved in 8ml of DMSO, poured onto a glass plate, dried overnight at 90 ℃ and subsequently dried under vacuum at 80 ℃ for 1d to obtain a transparent proton exchange membrane. At room temperature, the film prepared was at 0.5M H2SO4Soaking for 24h, and washing with ultrapure water repeatedly until pH is 7. The average thickness of the film in the dry state is about 40 μm.
In the specific embodiment provided by the invention, the thermal stability test process of the proton exchange membrane is to test the thermal property of the proton exchange membrane by adopting a thermogravimetric analysis (TGA), and the model of the used instrument is SDT TA instruments 2960Simultaneous DTA-TGA. The heating rate is 10.00 ℃ for min-1The temperature was raised to 600 ℃ under a nitrogen atmosphere. The samples were dried under vacuum at 140 ℃ for 6h before measurement.
The proton exchange membrane test method in the embodiment provided by the invention is ASTM D882 REF ASTM, and the tensile strength and elongation of the proton exchange membrane are tested by adopting an Instron Universal Materials Testing System (model 5544) mechanical tensile tester, wherein the load is 10N, the temperature is 25 ℃, the relative humidity is 50 percent, the film is cut into a rectangle with the thickness of 10mm × 40mm, and the thickness of a test sample is tested by adopting a digital micrometer with the precision of 1 mu m and the sensitivity of 40 percent.
The water absorption and water swelling performance test method of the proton exchange membrane in the embodiment provided by the invention comprises the steps of soaking the proton exchange membrane in ultrapure water for 24 hours at room temperature, and then removing water with paper to weigh the proton exchange membrane into Wwet. Subsequently, the film was dried under vacuum at 120 ℃ for 24 hours and weighed as Wdry. Water Uptake (WU) of the proton exchange membrane was calculated according to the following equation:
Figure GDA0002472518120000062
cutting proton exchange membrane with fixed size (4cm × 1cm), soaking in ultrapure water for 24 hr, and measuring length (L)wet) Length (L) measured after vacuum drying at 120 ℃ for 24hdry). Water Swelling (WS) of the proton exchange membrane was calculated according to the following equation:
Figure GDA0002472518120000071
the Ion Exchange Capacity (IEC) test process of the proton exchange membrane in the specific implementation example provided by the invention is that 0.1-0.2g of the proton exchange membrane is soaked in 100ml of 1M HCl for 24H and then soaked in 100ml of 1M NaCl for 24H, so that H in sulfimide+With Na+The exchange is complete. H is measured by 0.01M NaOH titration+Phenolphthalein as an indicator. The IEC of the proton exchange membrane was calculated according to the following equation:
Figure GDA0002472518120000072
VNaOHand [ NaOH]The volume and concentration of the NaOH solution, respectively, and W is the mass of the proton exchange membrane.
The proton conductivity of the proton exchange membrane is measured by a four-electrode method, and the Electrochemical Impedance Spectroscopy (EIS) is measured by using a constant voltage-constant current AUTO L AB model PGSTAT12/30/302, the frequency range is 1Hz-4MHz, and the oscillating voltage is5 mV. Before testing, the films were soaked in 1M hydrochloric acid for 48h and then rinsed with deionized water until the pH was 7. The conductivity measurement temperature range is 30-80 deg.C, the interval is 10 deg.C, and the relative humidity is lower than 100%. Proton conductivity (σ, S cm) was calculated from the impedance data according to the following equation-1):
Figure GDA0002472518120000073
d is a distance (cm) between electrodes, t and w are a thickness (cm) and a width (cm) of the film, and R is a resistance (Ω) obtained from the impedance data.
FIG. 1: schematic drawing of hanging long/short side chain of proton acid to proton exchange membrane: (a)
Figure GDA0002472518120000074
a sandwich structure proton conduction model schematic diagram of the structure, (b) a wide proton channel formed by long/short side chains, (c) a narrow proton channel formed by short side chains, (d) a narrow proton channel formed by long side chains, and (e) a specific implementation example of a long/short side chain proton exchange membrane molecular structure.
FIG. 2 a: example infrared spectroscopy of proton exchange membranes. 3400cm-1(a) The formation of polyamide was confirmed by stretching and contraction of the N-H bond of the amino group corresponding to the characteristic peak at 3300cm-1(b) The characteristic peak corresponds to the stretching vibration of the N-H bond of the sulfonimide. 3000-3100cm-1(c) The absorption band is caused by carbon-hydrogen bond stretching vibration of aromatic ring and 2800-3000cm-1(d) The characteristic peak corresponds to the stretching vibration of the fatty alkyl chain C-H. Typical absorption bands for S ═ O and S-O in sulfonimide groups appear at 1355--1(e)。
FIG. 2 b: examples of proton exchange membranes1H NMR spectrum. Hydrophobic Hydrogen (H) of all proton exchange membranesato Hg) Hydrogen (H) clearly appears in the spectrumnto Ht) Appearing in the long side chain proton exchange membrane-0.49 but not in the short side chain proton exchange membrane-0.49, clearly indicating that it belongs to the BPSIIA branch chain. Meanwhile, short side chain proton exchange membrane-0.49 sulfonic acid proton (H)hto Hk) Can be clearly distinguished. Long and longThe proton peaks in/short side proton exchange membrane-0.49 and long/short side proton exchange membrane-0.67 confirm the presence of sulfonic acid groups and BPSIIA groups.
FIG. 3: TGA curves of the proton exchange membranes of the examples were carried out. The mass loss around 100 ℃ is caused by water volatilization, and the mass loss before 200 ℃ is caused by volatilization of the high melting point organic solvent (NMP) remaining in the polymer. There are two degradation steps at 200-. The styrene-based radicals and the hydrogen on the polymer chain react at 450-500 ℃ resulting in the destruction of the polymer backbone. The thermal stability of the PEM prepared in the experiment reached 200 ℃ which exceeded the application requirements of PEM fuel cells (about 80 ℃).
FIG. 4: examples of proton exchange membranes and
Figure GDA0002472518120000081
117 tensile strength and elongation. The mechanical stability of the prepared proton exchange membrane is 23-53MPa and is higher than that of the proton exchange membrane
Figure GDA0002472518120000082
117, indicating that the prepared proton exchange membrane has proper mechanical stability and can be applied to PEM fuel cells. In addition, the polymer containing the sulfonimide group has superior mechanical properties to the polymer containing the sulfonic acid group. It can also be seen from the figure that the elongation at break of the film is significantly less than
Figure GDA0002472518120000083
117, indicating a smaller deformation ratio during Membrane Electrode Assembly (MEA) fabrication.
FIG. 5: examples of proton exchange membranes and
Figure GDA0002472518120000084
water absorption and swelling ratio of 117. According to the layered model, the water absorption and swelling ratio directly reflects the proton transport channel size of the membrane. When at the same IEC level, the short side chain proton exchange membrane-0.49 and the long side chain proton exchange membrane-049 have similar characteristicsWater uptake of 7.38 wt.% and 7.52 wt.%, respectively. In contrast, the long/short side chain proton exchange membrane-0.49 membrane exhibited a higher water uptake of 9.10 wt.%. If the relationship between hydration (water molecules adsorbed at each proton site) and structural change (swelling) is used to study the state of the corresponding water and water/proton transport in the PEM. The hydration for the long side chain proton exchange membrane and the short side chain proton exchange membrane were the same (═ 11), the structural changes were similar (1.27% vs 1.35), while the long/short side chain proton exchange membrane had higher hydration (═ 13) and structural changes (4.77%). It can be concluded that the long/short side chain structure results in the long/short side chain proton exchange membrane forming a wider proton transport channel, leading to a significant increase in structural variation. Further, when the IEC value was increased to 0.67, the water uptake and structural change of the long/short side chain proton exchange membrane increased to 13.51 wt% and 6.58%, respectively. When in use
Figure GDA0002472518120000085
117 had the same hydration (═ 13), the structural change of the long/short side chain proton exchange membrane was smaller (6.58% vs. 10.5%, as in table 1), indicating that the polyamide proton exchange membrane had excellent dimensional stability in water.
FIG. 6 proton conductivity of proton exchange membrane in examples of implementation the proton conductivity of proton exchange membrane varies with temperature as shown in FIG. 6 and Table 3 the proton conductivity depends on the hydrophilic groups (IEC values) of the polymer polymers having the same hydrophilic and hydrophobic components, such as long side chain proton exchange membrane-0.49, short side chain proton exchange membrane-0.49 and long/short side chain proton exchange membrane-0.49, so they should have similar proton conductivity, however, the proton conductivity of long/short side chain proton exchange membrane-0.49 is about twice as high as that of short side chain proton exchange membrane-0.49 and long side chain proton exchange membrane-0.49 (as shown in FIG. 6), which is related to L SPA-0.49 having wider proton transfer channels, furthermore, when the IEC value of long/short side chain exchange membrane is increased to 0.67, the maximum proton conductivity reaches 0.067S cm at 80 deg.C-1. But still below
Figure GDA0002472518120000091
117 two orders of magnitude, mainly due to the low IEC values associated with proton exchange membrane membranes (0.67vs. 0.91). However, compared to the recently reported sulfonimide functionalized PEMs, the proton conductivity is much lower than that of the proton exchange membranes prepared by the present invention, although the IEC value is 3 times higher than that of the PEM. The results show that the method greatly increases the 'bulk water' (water absorption) in the long/short side chain proton exchange membrane, and the membrane forms an excellent proton transmission channel and enhances the proton conductivity.

Claims (7)

1. A proton exchange membrane with polyamide resin as a polymer skeleton is characterized in that the molecular structural formula of the polymer is as follows:
Figure DEST_PATH_IMAGE001
。
2. the proton exchange membrane according to claim 1 wherein the molecular weight of said polymer ranges from tens of thousands to hundreds of thousands.
3. A method for synthesizing a proton exchange membrane according to claim 1, wherein the method comprises the step of heating, dehydrating and polycondensing a diamino compound and a dicarboxy compound in a polar solvent.
4. The synthesis method of claim 3, wherein the polar solvent is N-methylpyrrolidone, and the reaction system further comprises pyridine, triphenyl phosphite and a metal salt system.
5. The method of claim 4, wherein pyridine and triphenyl phosphite function as catalysts.
6. The method of claim 4, wherein the metal salt is selected to increase the solubility of the polymer and the metal salt is CaCl2，LiCl，KSCN，MgCl2Or ZnCl2。
7. The synthesis method according to claim 3, wherein the temperature range of the heating dehydration polycondensation is 90-110 ℃, and the reaction time is more than 6 hours.
CN201610297297.1A 2016-05-05 2016-05-05 Proton exchange membrane and synthesis method and application thereof Active CN107346829B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610297297.1A CN107346829B (en) 2016-05-05 2016-05-05 Proton exchange membrane and synthesis method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610297297.1A CN107346829B (en) 2016-05-05 2016-05-05 Proton exchange membrane and synthesis method and application thereof

Publications (2)

Publication Number Publication Date
CN107346829A CN107346829A (en) 2017-11-14
CN107346829B true CN107346829B (en) 2020-07-10

Family

ID=60253834

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610297297.1A Active CN107346829B (en) 2016-05-05 2016-05-05 Proton exchange membrane and synthesis method and application thereof

Country Status (1)

Country Link
CN (1) CN107346829B (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108199066A (en) * 2018-01-16 2018-06-22 成都新柯力化工科技有限公司 A kind of fuel cell covalent organic framework proton exchange membrane and preparation method
CN110739478B (en) * 2019-11-07 2022-05-17 大连理工大学 Preparation method of long-short side chain blended anion exchange membrane
CN111303436B (en) * 2020-03-06 2022-03-18 珠海冠宇电池股份有限公司 Polyolefin-g-hyperbranched polybenzimidazole graft copolymer and preparation method and application thereof
CN114614058B (en) * 2020-12-04 2024-05-07 中国石油化工股份有限公司 Thin-layer composite proton exchange membrane and preparation method and application thereof
CN114824393B (en) * 2021-01-29 2024-01-30 武汉氢阳能源有限公司 Quaternary amine salt composite proton exchange membrane and preparation method thereof
CN115020771B (en) * 2022-05-07 2024-03-15 中国地质大学（武汉） HBM blending modified PBI proton exchange membrane and preparation method and application thereof

Also Published As

Publication number Publication date
CN107346829A (en) 2017-11-14

Similar Documents

Publication Publication Date Title
CN107346829B (en) Proton exchange membrane and synthesis method and application thereof
Wang et al. Acid-base membranes of imidazole-based sulfonated polyimides for vanadium flow batteries
Yang et al. Influences of the structure of imidazolium pendants on the properties of polysulfone-based high temperature proton conducting membranes
Karlsson et al. Polysulfone ionomers for proton-conducting fuel cell membranes: sulfoalkylated polysulfones
Gao et al. Sulfonation of poly (phthalazinones) with fuming sulfuric acid mixtures for proton exchange membrane materials
Zhang et al. Synthesis and properties of reprocessable sulfonated polyimides cross-linked via acid stimulation for use as proton exchange membranes
Lee et al. Preparation and evaluation of sulfonated-fluorinated poly (arylene ether) s membranes for a proton exchange membrane fuel cell (PEMFC)
Chen et al. Crosslinked sulfonated poly (arylene ether ketone) membranes bearing quinoxaline and acid–base complex cross-linkages for fuel cell applications
Kawahara et al. Synthesis and proton conductivity of sulfopropylated poly (benzimidazole) films
Seo et al. Preparation and characterization of sulfonated amine-poly (ether sulfone) s for proton exchange membrane fuel cell
Li et al. A novel sulfonated poly (ether ether ketone) and cross-linked membranes for fuel cells
Wang et al. Highly compatible acid–base blend membranes based on sulfonated poly (ether ether ketone) and poly (ether ether ketone-alt-benzimidazole) for fuel cells application
Han et al. Considerations of the morphology in the design of proton exchange membranes: cross-linked sulfonated poly (ether ether ketone) s using a new carboxyl-terminated benzimidazole as the cross-linker for PEMFCs
Shin et al. Poly (p-phenylene)-based membrane materials with excellent cell efficiencies and durability for use in vanadium redox flow batteries
Yue et al. Phosphoric acid-doped organic-inorganic cross-linked sulfonated poly (imide-benzimidazole) for high temperature proton exchange membrane fuel cells
Dai et al. Soluble polybenzimidazoles incorporating Tröger’s base for high-temperature proton exchange membrane fuel cells
Ju et al. Construction of alkali-stable anion exchange membranes with hydrophilic/hydrophobic microphase separation structure by adjusting side chain length
US20080318109A1 (en) Method for the production of a sulfonated poly (1, 3, 4-oxadiazole) polymer
CA2602240A1 (en) Crosslinked polymer electrolyte and method for producing same
Wang et al. Sulfonated poly (phthalazinone ether sulfone) membrane as a separator of vanadium redox flow battery
Chen et al. Synthesis and study of pyridine-containing sulfonated polybenzimidazole multiblock copolymer for proton exchange membrane fuel cells
Bai et al. Proton exchange membranes based on sulfonated polyarylenethioethersulfone and sulfonated polybenzimidazole for fuel cell applications
Zhang et al. Fabrication of a polymer electrolyte membrane with uneven side chains for enhancing proton conductivity
Zhu et al. Hybrid proton conducting membranes based on sulfonated cross-linked polysiloxane network for direct methanol fuel cell
Chen et al. Quinoxaline-based crosslinked membranes of sulfonated poly (arylene ether sulfone) s for fuel cell applications

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant