CN107346829A - A kind of PEM and its synthetic method and application - Google Patents
A kind of PEM and its synthetic method and application Download PDFInfo
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- CN107346829A CN107346829A CN201610297297.1A CN201610297297A CN107346829A CN 107346829 A CN107346829 A CN 107346829A CN 201610297297 A CN201610297297 A CN 201610297297A CN 107346829 A CN107346829 A CN 107346829A
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- 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]
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- 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
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- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
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- 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
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- 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]
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- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
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Abstract
The invention discloses one kind to pass through the novel proton exchange membranes that are simultaneously suspended on the acid ion containing Bronsted acid on length/short-side chain.The advantages of such a structure design is that the Bronsted acid of length/short-side chain suspension is present in PEM simultaneously, expands distributed areas of the proton in PEM.Acid ion containing Bronsted acid after absorbing hydrone by that can increase proton transfer passage.The beneficial effects of the present invention are by the design of such a structure, continuous unimpeded proton transfer passage can be established preferably in PEM, be advantageous to improve proton conductivity, fuel cell is used for by PEM, the energy density of fuel cell, energy conversion efficiency will be significantly improved.
Description
Technical field
It is more particularly to a kind of to contain simultaneously the present invention relates to a kind of proton exchange membrane material available for fuel cell
The acid ion of Bronsted acid is suspended on the structure design of the PEM on long short-side chain and specific implementation is illustrated.
Background technology
Exploitation new material (such as catalyst and exchange membrane) and design new equipment model are pem fuel electricity
The significant challenge that pond (Proton Exchange Membrane Fuel Cells, PEMFCs) development faces.Proton is handed over
It is one of Proton Exchange Membrane Fuel Cells most critical part to change film (PEM), it is desirable to have high-quality electron conductivity,
Enough water absorbs, while has moderate swelling ratio.Perfluorosulfonic acid proton exchange film, such asIt can expire
Sufficient the demand, butWith permeable, higher compared with proton conductivity reduction, electric osmose under low humidity
The shortcomings of high cost and environment caused by fuel permeation rate, perfluor skeleton are unfriendly.Therefore, non-fluorine sulphur is developed
Acid ionomer membranes substituteIt is current study hotspot.But non-fluorine sulfonate film is in same ion
The problem of proton conductivity is low be present under exchange capacity (ion exchange capacity, IEC).One kind effectively carries
The method of high proton conductance is to increase the content (IEC values) of Bronsted acid in PEM, but high IEC
Excessive water can be caused to absorb and be seriously swelled, or even the problems of dissolution of film at high temperature occur.
In order to see clearly conduction mechanism of the proton in PEM, people are according to experimental result, it is proposed that several
Theoretical model is simulatedThe microscopic appearance of proton channel, for example, cluster cluster-network model, corynebacterium mould
Type and stratified model, these models etc..According toThe research discovery of microscopic appearance, the connection of water cluster
Property and hydrophilic site distribution it is most important to proton conductive, so by controlling the connective and hydrophilic of water cluster
It is to obtain new high proton conductance PEM that highly effective proton transfer passage is established in site distribution
It is crucial.Pan etc. establishes-OH transmission channels at a high speed by designing the structure of alkaline exchange membrane ion cluster,
With medium IEC values 1.0mmolg-1Polymer film at 80 DEG C electrical conductivity reach 0.1S cm-1.At it
In preceding work, we have designed and synthesized a series of rigid-flexible hybrid structure exchange membranes, and these PEM are
With excellent proton channel, wherein by increase, " (bulk water are to be located at water to bulk water " to flexible back bone
The water in cluster center, its transmit the speed of proton higher than " surface water ") improve water cluster in PEM
Size.
The content of the invention
The technical problem to be solved in the present invention is, by the design of molecular structure, effectively to establish in PEM
Proton transfer passage, to improve the proton conductivity of PEM.The invention provides one kind by drawing simultaneously
Enter to hang length/short-side chain of Bronsted acid into PEM, increase the passage of proton transfer with this, its structure
Schematic diagram is as shown in Figure 1.According toSandwich structure proton conduction model (as shown in Figure 1a),
In-SO3Foring width between H layers (shell) isProton channel (core).PEM electrical conductivity master
Will be by " bulk water " determine that " bulk water " can influence the size of proton translocation passage.Based on this,
We, which design, submits the hydrophilic radical of misconnection branch different length in main chain, come improve " bulk water " contents and
Proton conduction efficiency, as shown in Figure 1 b.With comprising only long side chain (Fig. 1 c) or short-side chain (Fig. 1 d)
PEM is compared, and the staggered polymer of length/short-side chain has broader proton transfer passage.
Brief description of the drawings
Fig. 1：Length/short-side chain of Bronsted acid is hung to PEM schematic diagram：(a)The sandwich knot of structure
Structure proton conduction model schematic diagram, the wide proton channel that (b) length/short-side chain is formed, the narrow matter that (c) short-side chain is formed
Subchannel, the narrow proton channel that (d) long side chain is formed, (e) length/short-side chain PEM molecular structure it is specific
Implementation example.
Fig. 2：(a) infrared spectrum of PEM and (b) in implementation example1H H NMR spectroscopies.
Fig. 3：The TGA curves of PEM in implementation example.
Fig. 4：In implementation example PEM and117 tensile strength and elongation.
Fig. 5：In implementation example PEM and117 water absorbs and swelling ratio.
Fig. 6：The proton conductivity of PEM in implementation example.
Embodiment
The present invention, but not limited to this are illustrated with embodiment below.
The invention provides it is a kind of using simultaneously by the acid ion containing Bronsted acid be suspended on length/short-side chain with
Polyamide is the application example of the PEM scheme of polymer backbone.In order to be presented the present invention's
Usefulness, while designed and synthesized the acid ion containing Bronsted acid and be suspended on long side chain and short-side chain respectively
PEM, its molecular structural formula are as follows.By FTIR,1HNMR and TGA characterizes its knot
Structure and hot property, there is provided the performance such as mechanical strength, water absorption, volumetric expansion and proton conductivity.As a result table
It is bright, in identical IEC values, the acid ion containing Bronsted acid is suspended on long short side while of the present invention
There is PEM on chain high water absorbability (" bulk water ") and larger volume expansion (to expand matter
Sub- transmission channel), show that it has wider proton transmitting channel.The acid ion containing Bronsted acid is hanged simultaneously
It is relatively low to hang over the swelling of the PEM on length/short-side chain, shows than business117 more preferable chis
Very little and mechanical stability, proton conductivity is close to 10-1S cm-1, far above long side chain protons exchange membrane and short side
Chain PEM.
The molecular structure of PEM in practicing
It is used for the molecular structure of long side chain and short-side chain PEM contrasted in practicing
The material used in specific implementation example provided by the invention include benzsulfamide (Sigma-Aldrich),
P-toluenesulfonylchloride (p-methyl benzene sulfonic chloride) (Sigma-Aldrich), dimethyl
5-aminoisophthalate (5- amino isophthalic acids dimethyl ester) (Sigma-Aldrich), potassium permanganate
(GCE), Lithium hydroxide monohydrate (Alfa-Aesar), triphenyl phosphite (TPP) (Alfa-Aesar) and sodium chloride
(Alfa-Aesar).4,4 '-(9-fluorenylidene) dianiline (double (4- aminophenyls) fluorenes of 9,9-) (FIDA)
(Sigma-Aldrich), decanedioic acid (DDA) (Sigma-Aldrich), 2,4-diaminobenzenesulfonic acid
(2,4- diamino benzene sulfonic acids) (DBSA) (Sigma-Aldrich), calcium chloride (GCE) and lithium chloride
(Sigma-Aldrich) used after being dried in vacuo 24h at 100 DEG C.Pyridine is dried with KOH.
N-methyl-2-pyrrolidone (1-METHYLPYRROLIDONE) (NMP) uses P2O5And CaCl2Dry,
24h is dried in vacuo at 180 DEG C.Deuterium dimethyl sulfoxide (DMSO) (Cambridge Isotope Laboratories)
Characterized for NMR.
PEM synthesis step is as shown in figure 4, concrete operations in specific implementation example provided by the invention
Journey is a certain amount of FIDA, DDA, DBSA, BPSIIA, TPP and LiCl mixtures are added to NMP
In pyridine, 100 DEG C are reacted 12h in a nitrogen atmosphere.Then mixture is cooled to 70 DEG C, be transferred to
Stirred in cold methanol, obtain solid white polymer precipitation.After white precipitate is filtered, repeatedly with first alcohol and water
Cleaning, finally it is dried in vacuo 24h at 140 DEG C.The scope of matter average molecular weight (Mw) is 235000-309000
G/mol, polydispersity index is close to 1 (table).The elementary analysis result of polymer matches with theoretical value (table 2),
Show successfully to have synthesized designed polymer.
PEM synthesis step in example is embodied
The molecular weight of the polymer dielectric of table 1
aTest at room temperature, DMF makees solvent, and polystyrene makees standard substance
The elementary analysis of the polymer dielectric of table 2
The preparation process of PEM is using solution-cast legal system in specific implementation example provided by the invention
Standby PEM, solvent is used as using dimethyl sulfoxide (DMSO).0.25g polymer dielectric is dissolved in
In 8ml DMSO, it is poured on glass plate, it is dried overnight at 90 DEG C, then, the vacuum at 80 DEG C
1d is dried, obtains transparent PEM.At room temperature, the film of preparation is in 0.5M H2SO4Middle leaching
24h is steeped, is then washed repeatedly with ultra-pure water until pH value is 7.About 40 μm of the average thickness of dry state film.
The heat stability testing process of PEM is using thermogravimetric in specific implementation example provided by the invention
Analytic approach (TGA) tests the hot property of PEM, uses the model SDT TA instruments of instrument
2960 Simultaneous DTA-TGA.10.00 DEG C of min of heating rate-1, it is warming up in a nitrogen atmosphere
600℃.Sample is dried in vacuo 6h at 140 DEG C before measurement.
The method of testing of PEM is ASTM D882 REF in specific implementation example provided by the invention
ASTM, tested using Instron Universal Materials Testing System (model 5544) mechanical stretching
Instrument tests the tensile strength and elongation of PEM.Its load is 10N, and temperature is 25 DEG C, relatively wet
Spend for 50%.Film is cut into 10mm × 40mm rectangle, uses precision as 1 μm, sensitivity 40%
Digital micrometer test sample thickness.
The water of PEM absorbs and water-swellable performance test methods in specific implementation example provided by the invention
At room temperature, PEM to be immersed in into 24h in ultra-pure water, then its weight is referred to as with paper removing water
Wwet.Then, its weight is referred to as W after the film being dried in vacuo into 24h at 120 DEG Cdry.According to lower section
The water that journey calculates PEM absorbs (WU):
The PEM of fixed dimension (4cm × 1cm) is cut, 24h is first soaked in ultra-pure water, measures length
(Lwet).Length (L is measured after 24h is dried in vacuo at 120 DEG Cdry).Proton exchange is calculated according to below equation
Water-swellable (WS) of film:
Ion exchange capacity (IEC) test process of PEM is in specific implementation example provided by the invention
0.1-0.2g PEMs are first soaked into 24h in 100ml 1M HCl, then in 100ml 1M NaCl
Middle immersion 24h so that the H in sulfimide+With Na+Exchange complete.Titrated and surveyed using 0.01MNaOH
Measure H+Quantity, phenolphthalein is as indicator.The IEC of PEM is calculated according to below equation:
VNaOH[NaOH] is respectively the volume and concentration of NaOH solution, and W is the quality of PEM.
The method of testing of the proton conductivity of PEM is proton in specific implementation example provided by the invention
The proton conductivity of exchange membrane is measured by four electrode method, and electrochemical impedance spectroscopy (EIS) uses constant pressure-constant current
AUTOLAB models PGSTAT12/30/302 is determined, frequency range 1Hz-4MHz, oscillating voltage 5mV.
Before test, film is soaked into 48h in 1M hydrochloric acid, then with deionized water rinsing until pH value is 7.
30-80 DEG C of conductivity measurement temperature range, 10 DEG C are spaced, relative humidity is less than 100%.According to lower section
Journey calculates proton conductivity (σ, S cm by impedance data-1):
D is the thickness (cm) and width (cm) that the distance between electrode (cm), t and w are film, and R is to be obtained from impedance data
The resistance (Ω) arrived.
Fig. 1：Length/short-side chain of Bronsted acid is hung to PEM schematic diagram：(a)Sanming City of structure
Control structure proton conduction model schematic diagram, the wide proton channel that (b) length/short-side chain is formed, what (c) short-side chain was formed
Narrow proton channel, the narrow proton channel that (d) long side chain is formed, (e) length/short-side chain PEM molecular structure
Specific implementation citing
Fig. 2 a：The infrared spectrum of PEM in implementation example.3400cm-1(a) characteristic peak at place corresponds to ammonia
The stretching vibration of the N-H keys of base, it was demonstrated that the formation of polyamide, and 3300cm-1(b) characteristic peak corresponds to sulphur
The stretching vibration of acid imide N-H keys.3000-3100cm-1(c) absorption bands is stretched by the C-H bond of aromatic rings
Caused and 2800-3000cm is vibrated in contracting-1(d) characteristic peak corresponds to aliphatic alkyl chain C-H stretching vibration.
S=O and S-O typical absorption band appears in 1355-1050cm in sulfimide moiety-1(e)。
Fig. 2 a：PEM in implementation example1H NMR spectras.Hydrophobic hydrogen (the H of all PEMsa
to Hg) clearly appear in spectrogram, hydrogen (Hn to Ht) appear in long side chain protons exchange membrane -0.49 and do not occur
In short-side chain PEM -0.49, clearly illustrate that it belongs to BPSIIA side chains.Meanwhile short-side chain proton
Sulfonic acid proton (the H of exchange membrane -0.49h to Hk) can clearly distinguish.Length/short-side chain PEM -0.49 and length
Proton peak in/short-side chain PEM -0.67 confirms the presence of sulfonic acid group and BPSIIA groups.
Figure:3：The TGA curves of PEM in implementation example.Mass loss near 100 DEG C is waved by water
It has been carried out the coffin upon burial that, and the mass loss before 200 DEG C is the organic solvent with high melting point (NMP) by being remained in polymer
Caused by volatilization.The degraded of two steps is there are at 200-280 DEG C and 350-500 DEG C, it is due to carbon that the first step, which is decomposed,
Sulfur bonds, produce styryl, sulphonyl and sulfonic acid free radical.On styryl free radical and polymer chain
Hydrogen reacts at 450-500 DEG C, causes the destruction of polymer backbone.The PEM prepared in experiment heat
Stability reaches 200 DEG C, more than the application requirement (about 80 DEG C) of PEM fuel cell.
Fig. 4：In implementation example PEM and117 tensile strength and elongation.The matter of preparation
The mechanical stability of proton exchange is 23-53MPa, is higher than117, show the proton exchange prepared
Film has suitable mechanical stability, can apply to PEM fuel cell.In addition, contain sulfimide base
The polymer of group has more superior mechanical property than the polymer containing sulfonic acid group.From figure it can also be seen that
The elongation at break of film is significantly less than117, show in membrane electrode assembling (MEA) manufacturing process tool
There is less deformation rate.
Fig. 5：In implementation example PEM and117 water absorbs and swelling ratio.According to stratiform mould
Type, water absorb the proton transmitting channel size for directly reflecting film with swelling ratio.When in same IEC levels,
There is similar water to absorb for short-side chain PEM -0.49 and long side chain protons exchange membrane -049, and respectively 7.38
Wt.% and 7.52wt.%.By contrast, the film of length/short-side chain PEM -0.49 shows higher water suction
Receive 9.10wt.%.If with aquation (hydrone that each proton site is adsorbed) and structure change (swelling)
Between relation be used for study in PEM if the state and water/proton transport of corresponding water.Long side chain protons exchange
Film is identical with the aquation of short-side chain PEM film (=11), and structure change is similar (1.27%vs 1.35),
And length/short-side chain PEM has higher aquation (=13) and structure change (4.77%).It can obtain
Go out, length/short side chain structure causes length/short-side chain PEM to form wider proton transmitting channel, causes
The significantly increasing of structure change.In addition, when IEC values are increased to 0.67, length/short-side chain PEM
Water absorb and structure change increase respectively to 13.51wt% and 6.58%.When117 have identical
During aquation (=13), structure change smaller (6.58%vs.10.5%, such as table of length/short-side chain PEM
1), show that polyamide PEM has excellent dimensional stability in water.
Fig. 6：The proton conductivity of PEM in implementation example.The proton conductivity of PEM is with temperature
The change of degree is as shown in Fig. 6 and table 3.Proton conductivity depends on the hydrophilic radical (IEC values) of polymer.Base
Have identical hydrophilic and hydrophobic constituent element in the polymer of identical skeleton, such as long side chain protons exchange membrane -0.49,
Short-side chain PEM -0.49 and length/short-side chain PEM -0.49, thus they should have it is similar
Proton conductivity.Handed over however, the proton conductivity of length/short-side chain PEM -0.49 is approximately short-side chain proton
Twice (as shown in Figure 6) of film -0.49 and long side chain protons exchange membrane -0.49 is changed, this has with LSPA-0.49
Wider proton transmitting channel is relevant.In addition, when the IEC values of length/short-side chain PEM film increase to 0.67
When, highest proton conductivity reaches 0.067S cm at 80 DEG C-1.But it is less than117 two
The order of magnitude, mainly due to the IEC values of PEM film low relevant (0.67vs.0.91).But with report recently
The sulfimide functionalization PEM in road is compared, although its IEC value is 3 times of this paper, however, its proton is electric
Conductance is well below the PEM prepared using the present invention.The above results show that this method considerably increases
In length/short-side chain PEM film " bulk water " (water absorption), it is excellent to show that the film forms
Proton transmitting channel, enhance proton conductivity.
Claims (20)
1. a kind of PEM, its structure composition includes macromolecular scaffold, long side chain, short-side chain and contains
The acid ion of Bronsted acid, described PEM are structurally characterized in that the acid group containing Bronsted acid
Ion is suspended on length/short-side chain simultaneously, and length/short-side chain is connected on macromolecular scaffold.
2. according to claim 1 be suspended on length/short-side chain with the acid ion containing Bronsted acid simultaneously
Novel proton exchange membranes, it is characterised in that described macromolecular scaffold structure can be it is linear, it is three-dimensional
It is or hyperbranched.
3. according to claim 1 be suspended on length/short-side chain with the acid ion containing Bronsted acid simultaneously
Novel proton exchange membranes, it is characterised in that described high-molecular bone frame material includes the poly- second of perfluor
The resin of olefine resin, partially fluorinated polyvinyl resin and nonfluorinated.
4. according to claim 3 be suspended on length/short-side chain with the acid ion containing Bronsted acid simultaneously
Novel proton exchange membranes, it is characterised in that the resin of described nonfluorinated includes polyether-ether-ketone resin,
Polyethersulfone resin, polyphenylene sulfide, polystyrene resin, polyphosphazene resin, polybenzimidazoles
Resin, polyimide resin and polyamide.
5. according to claim 1 be suspended on length/short-side chain with the acid ion containing Bronsted acid simultaneously
Novel proton exchange membranes, it is characterised in that described short-side chain includes phenyl ring, the carbochain of 1-3 carbon,
O, N, S and halogen atom, amino, aliphatic radical, amide groups, imide or acid ion are direct
It is connected on macromolecular scaffold.
6. according to claim 1 be suspended on length/short-side chain with the acid ion containing Bronsted acid simultaneously
Novel proton exchange membranes, it is characterised in that described long side chain includes the carbon for being more than 4 carbon atoms
Chain, more than the perfluor carbochain of 4 carbon atoms, more than the partially fluorinated carbochain of 4 carbon atoms,
Containing heteroatomic carbochain；There are phenyl ring, hydridization, hetero atom, amino, aliphatic radical, amide groups, acyl sub-
Amido, alkyl chain or the long-chain being combined into containing heteroatomic alkyl chain.
7. according to claim 1 be suspended on length/short-side chain with the acid ion containing Bronsted acid simultaneously
Novel proton exchange membranes, it is characterised in that described acid ion includes sulfonate radical, and double sulphonyl are sub-
Amine groups, phosphate radical.
8. it is suspended on length/short side with the acid ion containing Bronsted acid simultaneously according to claim 1-6
The novel proton exchange membranes of chain, it is characterised in that can by different macromolecular scaffolds, long short-side chain and
Acid ion, be combined using different molecular design methods, prepare with it is different composition and
The new proton exchange that length/short-side chain is suspended on the acid ion containing Bronsted acid simultaneously of structure
Film.
9. it is suspended on length/short-side chain with the acid ion containing Bronsted acid simultaneously described in a kind of claim 1
Novel proton exchange membranes application, it is characterised in that the application is, will contain matter simultaneously by a kind of
The functional group of sub- acid is suspended on polymer on long short-side chain as PEM, obtains a kind of water
The electrolyte of electrolysis.
10. a kind of polyamide is the PEM of polymer backbone, it is characterised in that the polyamide gathers
The molecular structural formula of compound is as follows：
Z is various aliphatic alkyl chains, aromatic hydrocarbon, containing heteroatomic aliphatic alkyl chain, containing heteroatomic virtue
Fragrant hydro carbons, condensed ring, bridged ring, spiro-compound, aromatic hydrocarbon, condensed ring, bridge containing three or more number carboxylic acids
Ring, spiro-compound；
R1Can be H, F, Cl, Br, I, NO2, OH, NH2, saturation or unsaturated alkyl, carbonyl, carboxylic
Base, ester group, sulfonic group and cyano group；
R2Can be H, F, Cl, Br, I, NO2, OH, NH2, saturation or unsaturated alkyl, carbonyl, carboxylic
Base, ester group, sulfonic group and cyano group；
R3Can be H, F, Cl, Br, I, NO2, OH, NH2, saturation or unsaturated alkyl, carbonyl, carboxylic
Base, ester group, sulfonic group and cyano group；
R4Can be H, F, Cl, Br, I, NO2, OH, NH2, saturation or unsaturated alkyl, carbonyl, carboxylic
Base, ester group, sulfonic group and cyano group.
11. according to the PEM described in claim 1-10, described PEM is with polyamide resin
Fat is suspended on the new of length/short-side chain for polymer backbone with the acid ion containing Bronsted acid simultaneously
Type PEM, it is characterised in that high-molecular bone frame material is polyimide resin, and Bronsted acid is
Sulfonic acid and double sulfimides.
12. according to the PEM described in claim 1-10, described PEM is with polyamide resin
Fat is suspended on the new of length/short-side chain for polymer backbone with the acid ion containing Bronsted acid simultaneously
Type PEM, it is characterised in that polyimide resin passes through two kinds of binary amine presomas and two
Kind dicarboxylic acids class presoma polymerize and obtained under certain reaction condition；One of which diamine
Class presoma is the aromatic compound containing sulfonic acid, and wherein proton is connected to apart from macromolecular scaffold
On nearer side chain.One of which dicarboxylic acids class presoma is the compound containing double sulfimides,
Wherein proton is connected on macromolecular scaffold side chain farther out.
13. according to the PEM described in claim 1-10, described PEM is with polyamide resin
Fat is suspended on the new of length/short-side chain for polymer backbone with the acid ion containing Bronsted acid simultaneously
Type PEM.
14. according to the PEM described in claim 1-10, described PEM is with polyamide resin
Fat is suspended on the new of length/short-side chain for polymer backbone with the acid ion containing Bronsted acid simultaneously
Type PEM, it is characterised in that proton can adjust by the content for adjusting the acid precursor containing proton
The ion exchange capacity of exchange membrane.
15. according to the PEM described in claim 1-10, described PEM is with polyamide resin
Fat is suspended on the new of length/short-side chain for polymer backbone with the acid ion containing Bronsted acid simultaneously
Type PEM, it is characterised in that the molecular weight ranges of its polymer are tens of thousands of to hundreds of thousands.
A kind of a kind of 16. synthesis with the PEM for increasing proton transfer passage described in claim 1-10
Method, it is characterised in that this method is in pole by double amino compounds and double carboxyl compounds
Property solvent in carry out thermal dehydration polycondensation, the functional group is respectively carboxylic acid group and amino.
17. synthetic method according to claim 15, it is characterised in that reaction system is N- methylpyrroles
Alkanone, pyridine, triphenyl phosphite and metal salt system.
18. synthetic method according to claim 15, it is characterised in that its pyridine and triphenyl phosphite
Play catalyst action.
19. synthetic method according to claim 15, it is characterised in that it is molten that metal salt plays increase polymer
The effect of solution property, described metal salt can be CaCl2Or LiCl, KSCN, MgCl2, ZnCl2
Deng.
20. synthetic method according to claim 15, it is characterised in that the humidity province of thermal dehydration polycondensation
Between be 90~110 DEG C, the reaction time is more than 6 hours.
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