CN108649256A - The preparation method and application of sulfonate polybenzimidazole proton exchange membrane - Google Patents
The preparation method and application of sulfonate polybenzimidazole proton exchange membrane Download PDFInfo
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- CN108649256A CN108649256A CN201810452145.3A CN201810452145A CN108649256A CN 108649256 A CN108649256 A CN 108649256A CN 201810452145 A CN201810452145 A CN 201810452145A CN 108649256 A CN108649256 A CN 108649256A
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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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- 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
- H01M8/1039—Polymeric electrolyte materials halogenated, e.g. sulfonated polyvinylidene fluorides
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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
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
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Abstract
A kind of polymer architecture general formula of sulfonate polybenzimidazole proton exchange membrane is as follows：The polymer is random copolymer, wherein 0<N≤0.8,0.2≤m<1, m+n=1, the weight average molecular weight of such polymer is between 5,000 800000；The present invention has the advantages that proton conductivity is high.
Description
Technical field
The polybenzimidazoles class proton exchange membrane containing sulfonic acid group that the present invention relates to a kind of, and it is applied to acidic electrolysis
In liquid flow battery.
Technical background
The mankind gradually accelerate the development and utilization of new energy, the suitable high-efficiency energy-storage technology of active demand.Acidic electrolysis
Liquid flow battery is a kind of large-scale electrochemical energy storage technology, system design mutual indepedent with capacitance of storage and power
Flexibly, the advantages that security performance is high, service life is long.And vanadium redox battery (VRB, abbreviation vanadium cell) is acid
Most there are foreground and a kind of representative energy storage technology in flow battery.
Electrolyte is the different vanadium ion sulfuric acid solution of valence state in vanadium cell, needs to separate using proton exchange membrane positive and negative
Pole electrolyte, while the channel of proton transport is provided to ensure the circuit of inside battery, therefore the performance of film directly affects vanadium
The performance of battery, to ensure vanadium cell effective use steady in a long-term, it is desirable that there is film good proton conductivity, lower vanadium to ooze
Saturating rate, stable chemical property and lower cost.Currently used commercialized proton exchange membrane is Dupont companies
Nafion membrane, perfluorinated sulfonic acid structure assign the chemical property of its stabilization and higher proton conductivity, but more serious vanadium infiltration
The industrial applications of Nafion membrane are limited with fancy price.So the matter of exploitation highly selective, high stability and low cost
Proton exchange is most important.
Polybenzimidazoles (PBI) is the aromatic heterocyclic polymer of the repetitive unit containing benzimidazole in high polymer main chain, armaticity
Main chain make it have compared with high mechanical stability and chemical stability.The ion-exchange group of PBI is located on main chain, imidazole ring
On nitrogen-atoms be easy to be protonated (J.Electrochem.Soc.1995,7,121-123) in acid condition, formed network
The electropositive structure of shape has the material base of proton conduction.In vanadium cell, positive and negative anodes electrolyte be different valence state vanadium from
The sulfuric acid solution of son, in this way, the PBI films of sulfuric acid doping be provided simultaneously with separate positive and negative anodes electrolyte, proton conducting and barrier vanadium from
The ability of son infiltration.Currently, commercialized polybenzimidazole resin is poly- [2,2 '-(- phenylene) -5,5 '-dibenzo miaows
Azoles].Its chemical structural formula is as follows：
Chanho Noh et al. are prepared for mPBI homogeneous proton exchange membrane for (Applied in all-vanadium flow battery
Materials＆Interfaces., 2017,9,36799-36809), but its acid doping amount is low, and proton conductivity is caused to reduce,
It is low to further result in cell voltage efficiency.Therefore the present invention takes the backbone structure of sulfonate polybenzimidazole, prepares ion exchange
Film is expected to the extensive use in acidic electrolysis bath flow battery.
Invention content
It is an object of the invention to synthesize a kind of preparation for the sulfonate polybenzimidazole proton exchange membrane that proton conductivity is high
Methods and applications.
Polybenzimidazoles main chain in the present invention contains sulfonic acid group, increases the conductive performance of proton.The present invention utilizes difference
The diacid of structure is prepared with biphenyl tetramine by nucleophilic condensation polymerization.The present invention has good application in vanadium battery field
Foreground.
To achieve the above object, the technical solution adopted by the present invention is：
A kind of polybenzimidazoles Type of Collective proton exchange membrane, polymer architecture general formula are as follows：
The polymer is random copolymer, wherein 0<N≤0.8,0.2≤m<1, m+n=1, the weight of such polymer is equal
Molecular weight is between 5000-800000；
R1 represents one of having structure：
R2 represents one of having structure：
Wherein：R3 and R4 is one kind in hydrogen atom, C1-C4 saturated alkanes group or C2-C4 unsaturation alkane groups,
R3 and R4 is identical or different group.
The preparation method of amberplex of the present invention, includes the following steps：
(1) diacid of the group containing R1 and the diacid and biphenyl tetramine of the group containing R2 are added in polyphosphoric acids,；Logical nitrogen
After oxygen in gas removing system, it is heated to 180-220 DEG C, reacts 4-48 hours, while hot pours into solution containing 2-8%
Sodium hydroxide solution at silk, be fully washed with water, until solution is in neutrality.Filtering, drying；Wherein diacid in reaction system
The monomer concentration of monomer and biphenyl tetramine in polyphosphoric acids solvent is between 2-15wt%, the diacid of the group containing R1 and base containing R2
The ratio between diacid mole dosage of group is 1：5~4：5, the diacid of the group containing R1 and the diacid total moles dosage and biphenyl of the group containing R2
The mole dosage of tetramine is identical；
(2) one or more polarity that the polymer of drying is dissolved in NMP, DMF, DMAc, DMSO at 100-150 DEG C are molten
In agent, the control of the concentration of solution is in 2-15wt%, by obtained polymer solution direct pouring on glass plate or stainless steel plate,
The dry 6-10h film forming at 60-100 DEG C, then 80-150 DEG C of vacuum drying 6-24h, obtains the friendship of sulfonate polybenzimidazole proton
Film is changed, the thickness of film is between 10-100 μm.
The application of sulfonate polybenzimidazole proton exchange membrane of the present invention, includes the following steps：
(1) sulfonate polybenzimidazole proton exchange membrane is immersed into 10-48h in sulfuric acid solution；The concentration of sulfuric acid solution is in 1-
Between 16mol/L；
(2) the sulfonate polybenzimidazole proton exchange membrane impregnated is loaded on liquid-flow energy storage battery with acidic electrolyte, by film
It is clipped between two graphite felt electrodes, then uses graphite electrode board clamping, then fixed with poly (methyl methacrylate) plate, make electricity using peristaltic pump
Solution liquid stream crosses film both sides, specific monocell assemble method see article (Energy Environ.Sci., 2011,4,1147-
1160, amberplex used for all-vanadium redox flow battery).
Liquid-flow energy storage battery with acidic electrolyte of the present invention includes：All-vanadium liquid flow energy storage battery, vanadium bromine liquid flow energy storage battery, vanadium
The redox flow batteries containing acidic electrolyte bath such as cerium liquid flow energy storage battery.
The present invention has the following advantages that compared with existing：
1, the synthetic operation for the polybenzimidazole polymer containing sulfonic acid group that the present invention synthesizes is simple, and the polymer contains
There is more sulfonic acid group, is conducive to the proton conductivity and hydrophily that improve film；
2, there is the amberplex obtained good thermal stability and mechanical performance, polymer decomposition temperature can reach
400-600 DEG C, tensile strength can reach 80-120MPa；
3, the amberplex, which is applied to vanadium redox battery, has excellent barrier vanadium ion permeance property,
Fig. 2 is the film and is commercialized the vanadium ion infiltration comparison of Nafion.
Description of the drawings：
Fig. 1 is the different current density (40-140mA/cm of polymer film prepared by example 32) under vanadium cell performance data；
Fig. 2 is the vanadium ion infiltration comparison of polymer film prepared by example 3 and commercialization Nafion212 films.
Specific implementation mode：
Following embodiment is the further explanation to the present invention, rather than is limited the scope of the invention.
Embodiment 1：
(1) 30g polyphosphoric acids (PPA) is added in the three-necked flask of 100ml, 5mmol biphenyl tetramines is added,
2.5mmol 5- sodium sulfonates-M-phthalic acid, 2.5mmol M-phthalic acids, monomer concentration 7wt% are passed through nitrogen, exclude three
Air in mouth bottle, is warming up to 180 DEG C, reacts 6h, stops stirring, pours into while hot in the sodium hydroxide solution of 2wt%, fully use
Water washing, until solution is in neutrality.Filtering, drying.
(2) polymer of preparation is dissolved in the solution for forming a concentration of 3wt% in nmp solvent at 100 DEG C, solution is poured
It casts onto on glass plate, is bulldozed with casting film knife.The dry 6h at 60 DEG C, then 80 DEG C of vacuum drying 6h, film is taken from glass plate
Under.It is about the polybenzimidazoles amberplex that 20 μm of sulfonation degrees are 50% to obtain thickness.
The application of sulfonate polybenzimidazole proton exchange membrane of the present invention, includes the following steps：
(1) sulfonate polybenzimidazole proton exchange membrane is immersed into 10h in 1mol/L sulfuric acid；
(2) the sulfonate polybenzimidazole proton exchange membrane impregnated is loaded on liquid-flow energy storage battery with acidic electrolyte, by film
It is clipped between two graphite felt electrodes, then uses graphite electrode board clamping, then fixed with poly (methyl methacrylate) plate, make electricity using peristaltic pump
Solution liquid stream crosses film both sides, specific monocell assemble method see article (Energy Environ.Sci., 2011,4,1147-
1160, amberplex used for all-vanadium redox flow battery).
In 40mA/cm2Under current density, the current efficiency of the sulfonate polybenzimidazole proton exchange membrane assembled battery is
99.2%, voltage efficiency 85.4%, energy efficiency 84.7%, under same current density, and the electricity of the mPBI films of unsulfonated
It is 97.6% to flow efficiency, and voltage efficiency is 80.0%, and energy efficiency is 78.1%, in contrast, the polybenzimidazoles matter of sulfonation
The cell voltage efficiency and energy efficiency of proton exchange assembling rise obviously, illustrate that the sulfonation of polybenzimidazoles effectively increases film
Proton-conducting, the internal resistance of cell is reduced, so that voltage efficiency is significantly improved.
Embodiment 2：
(1) 20g polyphosphoric acids (PPA) is added in the three-necked flask of 100ml, 5mmol biphenyl tetramines, 2mmol is added
5- sodium sulfonates-M-phthalic acid, 3mmol M-phthalic acids, monomer concentration 9.5wt% are passed through nitrogen, exclude in there-necked flask
Air is warming up to 190 DEG C, reacts 8h, stops stirring, pours into the sodium hydroxide solution of 4wt%, be fully washed with water while hot,
Until solution is in neutrality.Filtering, drying.
(2) polymer of preparation is dissolved in the solution that a concentration of 4wt% is formed in DMSO solvents at 110 DEG C, by solution
It is cast on glass plate, is bulldozed with casting film knife.The dry 8h at 70 DEG C, is then dried in vacuo 8h for 90 DEG C, by film from glass plate
It removes.It is about the polybenzimidazoles amberplex that 30 μm of sulfonation degrees are 40% to obtain thickness.
The application of sulfonate polybenzimidazole proton exchange membrane of the present invention, includes the following steps：
(1) sulfonate polybenzimidazole proton exchange membrane is immersed into 12h in 2mol/L sulfuric acid；
(2) the sulfonate polybenzimidazole proton exchange membrane impregnated is loaded on liquid-flow energy storage battery with acidic electrolyte, by film
It is clipped between two graphite felt electrodes, then uses graphite electrode board clamping, then fixed with poly (methyl methacrylate) plate, make electricity using peristaltic pump
Solution liquid stream crosses film both sides, specific monocell assemble method see article (Energy Environ.Sci., 2011,4,1147-
1160, amberplex used for all-vanadium redox flow battery).
In 40mA/cm2Under current density, the current efficiency of the sulfonate polybenzimidazole proton exchange membrane assembled battery is
98.9%, voltage efficiency 84.4%, energy efficiency 83.5%, under same current density, and the electricity of the mPBI films of unsulfonated
It is 97.6% to flow efficiency, and voltage efficiency is 80.0%, and energy efficiency is 78.1%, in contrast, the polybenzimidazoles matter of sulfonation
The cell voltage efficiency and energy efficiency of proton exchange assembling rise obviously, illustrate that the sulfonation of polybenzimidazoles effectively increases film
Proton-conducting, the internal resistance of cell is reduced, so that voltage efficiency is significantly improved.
Embodiment 3：
(1) 20g polyphosphoric acids (PPA) is added in the three-necked flask of 100ml, 5mmol biphenyl tetramines is added,
3,3 '-sodium disulfonate -4 2.5mmol, 4 '-biphenyl dicarboxylic acids, 2.5mmol M-phthalic acids, monomer concentration 12wt% are passed through
Nitrogen excludes the air in there-necked flask, is warming up to 200 DEG C, reacts 10h, stops stirring, pours into the sodium hydroxide of 6wt% while hot
It in solution, is fully washed with water, until solution is in neutrality.Filtering, drying.
(2) polymer of preparation is dissolved in the solution that a concentration of 5wt% is formed in DMSO solvents at 120 DEG C, by solution
It is cast on glass plate, is bulldozed with casting film knife.The dry 8h at 80 DEG C, then 100 DEG C of vacuum drying 10h, by film from glass plate
On remove.It is about the polybenzimidazoles amberplex that 40 μm of sulfonation degrees are 50% to obtain thickness.
The application of sulfonate polybenzimidazole proton exchange membrane of the present invention, includes the following steps：
(1) sulfonate polybenzimidazole proton exchange membrane is immersed into 14h in 4mol/L sulfuric acid；
(2) the sulfonate polybenzimidazole proton exchange membrane impregnated is loaded on liquid-flow energy storage battery with acidic electrolyte, by film
It is clipped between two graphite felt electrodes, then uses graphite electrode board clamping, then fixed with poly (methyl methacrylate) plate, make electricity using peristaltic pump
Solution liquid stream crosses film both sides, specific monocell assemble method see article (Energy Environ.Sci., 2011,4,1147-
1160, amberplex used for all-vanadium redox flow battery).
In 40mA/cm2Under current density, the current efficiency of the sulfonate polybenzimidazole proton exchange membrane assembled battery is
99.1%, voltage efficiency 85.4%, energy efficiency 84.6%, under same current density, and the electricity of the mPBI films of unsulfonated
It is 97.6% to flow efficiency, and voltage efficiency is 80.0%, and energy efficiency is 78.1%, in contrast, the polybenzimidazoles matter of sulfonation
The cell voltage efficiency and energy efficiency of proton exchange assembling rise obviously, illustrate that the sulfonation of polybenzimidazoles effectively increases film
Proton-conducting, the internal resistance of cell is reduced, so that voltage efficiency is significantly improved.
Embodiment 4：
With embodiment 3, different place is, 3,3 '-sodium disulfonate -4 1mmol, 4 '-biphenyl dicarboxylic acids are added
With 4,4 '-biphenyl dicarboxylic acids of 4mmol, the sulfonate polybenzimidazole amberplex that sulfonation degree is 20% is obtained.In 40mA/cm2
Under current density, the current efficiency of the sulfonate polybenzimidazole proton exchange membrane assembled battery is 98.8%, and voltage efficiency is
82.4%, energy efficiency 81.4%, under same current density, and the current efficiency of the mPBI films of unsulfonated is 97.6%, electricity
It is 80.0% to press efficiency, and energy efficiency is 78.1%, in contrast, the battery of the polybenzimidazoles proton exchange membrane assembling of sulfonation
Voltage efficiency and energy efficiency rise obviously, illustrate that the sulfonation of polybenzimidazoles effectively increases the proton-conducting of film, reduce
The internal resistance of cell, but its sulfonation degree is relatively low, compared with the high polybenzimidazoles proton exchange membrane of sulfonation degree, voltage efficiency under
Drop.
Embodiment 5：
(1) 15g polyphosphoric acids (PPA) is added in the three-necked flask of 50ml, 5mmol biphenyl tetramines, 2.5mmol is added
Sodium sulfonate -4 2-, 4 '-oxydibenzoic acids, 2.5mmol M-phthalic acids, monomer concentration 14.7wt% are passed through nitrogen, exclude
Air in there-necked flask is warming up to 210 DEG C, reacts 15h, stops stirring, pours into the sodium hydroxide solution of 8wt%, fill while hot
Divide and be washed with water, until solution is in neutrality.Filtering, drying.
(2) polymer of preparation is dissolved in the solution for forming a concentration of 6wt% in DMF solvent at 130 DEG C, solution is poured
It casts onto on glass plate, is bulldozed with casting film knife.The dry 5h at 90 DEG C, is then dried in vacuo 12h for 110 DEG C, by film from glass plate
It removes.It is about the polybenzimidazoles amberplex that 50 μm of sulfonation degrees are 50% to obtain thickness.
The application of sulfonate polybenzimidazole proton exchange membrane of the present invention, includes the following steps：
(1) sulfonate polybenzimidazole proton exchange membrane is immersed into 16h in 6mol/L sulfuric acid；
(2) the sulfonate polybenzimidazole proton exchange membrane impregnated is loaded on liquid-flow energy storage battery with acidic electrolyte, by film
It is clipped between two graphite felt electrodes, then uses graphite electrode board clamping, then fixed with poly (methyl methacrylate) plate, make electricity using peristaltic pump
Solution liquid stream crosses film both sides, specific monocell assemble method see article (Energy Environ.Sci., 2011,4,1147-
1160, amberplex used for all-vanadium redox flow battery).
In 40mA/cm2Under current density, the current efficiency of the sulfonate polybenzimidazole proton exchange membrane assembled battery is
99.2%, voltage efficiency 86.4%, energy efficiency 85.7%, under same current density, and the electricity of the mPBI films of unsulfonated
It is 97.6% to flow efficiency, and voltage efficiency is 80.0%, and energy efficiency is 78.1%, in contrast, the polybenzimidazoles matter of sulfonation
The cell voltage efficiency and energy efficiency of proton exchange assembling rise obviously, illustrate that the sulfonation of polybenzimidazoles effectively increases film
Proton-conducting, the internal resistance of cell is reduced, so that voltage efficiency is significantly improved.
Embodiment 6：
With embodiment 5, different place is, is added 2.5mmol 2- sodium sulfonate -4,4 '-oxydibenzoic acids and
4,4 '-oxydibenzoic acids of 2.5mmol, packed battery is tested under the same terms, current efficiency 99.0%, and voltage efficiency is
86.2%, energy efficiency 85.5% is almost the same with the sulfonate polybenzimidazole film of embodiment 5, the voltage efficiency than mPBI
With energy efficiency height.
Claims (5)
1. a kind of sulfonate polybenzimidazole proton exchange membrane, it is characterised in that its polymer architecture general formula is as follows：
The polymer is random copolymer, wherein 0<N≤0.8,0.2≤m<1, m+n=1, the Weight-average molecular of such polymer
Amount is between 5000-800000；
R1 is one of having structure：
R2 is one of having structure：
Wherein：R3 and R4 be hydrogen atom, C1-C4 saturated alkanes group or C2-C4 unsaturation alkane groups in one kind, R3 and
R4 is identical or different group.
2. a kind of preparation method of sulfonate polybenzimidazole proton exchange membrane as described in claim 1, it is characterised in that including
Following steps：
(1) diacid of the group containing R1 and the diacid and biphenyl tetramine of the group containing R2 are added in polyphosphoric acids,；Logical nitrogen removes
After removing the oxygen in system, it is heated to 180-220 DEG C, reacts 4-48 hours, solution is poured into the hydrogen containing 2-8% while hot
It at silk in sodium hydroxide solution, is fully washed with water, until solution is in neutrality.Filtering, drying；Wherein diacid monomer in reaction system
And monomer concentration of the biphenyl tetramine in polyphosphoric acids solvent be between 2-15wt%, the diacid of the group containing R1 and the group containing R2
The ratio between diacid mole dosage is 1：5~4：5, the diacid of the group containing R1 and the diacid total moles dosage and biphenyl tetramine of the group containing R2
Mole dosage it is identical；
(2) by the polymer of drying at 100-150 DEG C in molten polar solvent, the concentration control of solution in 2-15wt%, will
To polymer solution direct pouring on glass plate or stainless steel plate, the dry 6-10h film forming at 60-100 DEG C, then 80-
150 DEG C of vacuum drying 6-24h, obtain sulfonate polybenzimidazole proton exchange membrane, the thickness of film is between 10-100 μm.
3. a kind of preparation method of sulfonate polybenzimidazole proton exchange membrane as claimed in claim 2, it is characterised in that polarity
Solvent is the one or more of NMP, DMF, DMAc, DMSO.
4. a kind of application of sulfonate polybenzimidazole proton exchange membrane as described in claim 1, it is characterised in that including as follows
Step：
(1) sulfonate polybenzimidazole proton exchange membrane is immersed into 10-48h in sulfuric acid solution；The concentration of sulfuric acid solution is in 1-
Between 16mol/L；
(2) the sulfonate polybenzimidazole proton exchange membrane impregnated is loaded on liquid-flow energy storage battery with acidic electrolyte, film is clipped in
Between two graphite felt electrodes, graphite electrode board clamping is then used, then fixed with poly (methyl methacrylate) plate, make electrolyte using peristaltic pump
Flow through film both sides.
5. a kind of application of sulfonate polybenzimidazole proton exchange membrane as claimed in claim 4, it is characterised in that acidic electrolysis
Liquid liquid flow energy storage battery is all-vanadium liquid flow energy storage battery, siderochrome liquid flow energy storage battery, zinc bromine liquid flow energy storage battery, the storage of vanadium bromine liquid stream
One kind in energy battery, vanadium cerium liquid flow energy storage battery.
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