CN108878740A - A kind of non-ionic side chain modification polybenzimidazole membrane and preparation method thereof - Google Patents
A kind of non-ionic side chain modification polybenzimidazole membrane and preparation method thereof Download PDFInfo
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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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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- 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
- Y02E60/10—Energy storage using batteries
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- 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
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Abstract
The invention discloses a kind of non-ionic side chain modification polybenzimidazole membranes and preparation method thereof, belong to the preparation technical field of diaphragm used for all-vanadium redox flow battery.Non-ionic film suitable for all-vanadium flow battery, using polybenzimidazoles as main chain, membrane material is obtained after being grafted non-ionic side chain and is film-made, the chemical stability of film can be improved in film again while with high conductance, make film battery performance with higher, can be used as battery diaphragm and be applied in all-vanadium flow battery.
Description
Technical field
The invention belongs to the preparation technical fields of diaphragm used for all-vanadium redox flow battery, and in particular to a kind of non-ionic side chain is repaired
Adorn polybenzimidazole membrane and preparation method thereof.
Background technique
With the continuous development of the economy and society, more and more to the demand of the energy and consumption.Fossil energy faces exhaustion,
A large amount of consumption of fossil energy cause greenhouse effects and environmental pollution simultaneously, and energy problem and environmental crisis are increasingly prominent, energetically
Promote the development and utilization of the renewable and clean energy resources such as solar energy, wind energy imperative, the great attention increasingly by various countries.So
And the renewable energy such as solar energy, wind energy are because being influenced have unstable, discontinuous, uncontrollable unstable state special by Changes in weather
Point will cause great impact to the stability and safety of power grid.Extensive high-efficiency energy-storage technology and renewable energy power generation skill
Art is combined can improve the stability of electric system, improve the product of electric energy efficiently against the unstable state disadvantage of these energy
Matter, improves the utilization rate of the energy, while guaranteeing lasting energy supply and friendly ecological environment.Flow battery is because having circulation
The series of advantages such as the service life is long, environmentally protective, flexible design, operational safety, addressing freedom, scale easy to accomplish, become mesh
One of preceding of greatest concern, with fastest developing speed, energy storage technology of most prospect.
The core component of all-vanadium flow battery is electrode, electrolyte and amberplex.Wherein amberplex is core
One of heart component largely determines the service life of battery, performance, cost.Effect of the amberplex in all-vanadium flow battery
There are two main：One is separation positive and negative anodes electrolyte, prevents internal short-circuit of battery, avoids cross contamination；The other is conduction
Proton is connected to cell circuit.During all-vanadium flow battery runs or shelves, the vanadium ion of positive and negative electrode different valence state can pass through
Thus ionic membrane Cross slot interference can cause aqueous solvent to migrate and lead to the unbalance of positive and negative electrode electrolyte, substantially reduce all-vanadium flow
The energy efficiency and cycle life of battery.Now widely used commercialization amberplex is the Nafion of DuPont Corporation
Film, but it has the problems such as at high cost, vanadium infiltration is serious, water migration is serious.Therefore, a kind of low cost, long-life, height are developed
Ionic conductivity and highly selective amberplex are particularly important and our problems anxious to be resolved at present.
Summary of the invention
Present invention aim to ensure that improving the ability of chemical stability while polybenzimidazoles membrane mass transfer ability, one is provided
The preparation method of the non-ionic side chain modification polybenzimidazole membrane of kind：Use the polyphenyl with good thermal stability and mechanical performance
And imidazoles polymer, then grafting nonionic side chain is carried out to polymer and obtains the polybenzimidazoles and system of non-ionic side chain modification
Film.Prepared film has good chemical stability and higher ionic conductivity, can be applied in all-vanadium flow battery.
Technical solution of the present invention：
A kind of non-ionic side chain modification polybenzimidazole membrane, structural formula are as follows：
Wherein, x=0~1；Y=0~1；The positive integer that n is 2~10.
A kind of preparation method of non-ionic side chain modification polybenzimidazole membrane, steps are as follows：
(1) dissolution of polybenzimidazole polymer：Under inert gas protection, in 50~80 DEG C of oil bath pan by polyphenyl simultaneously
Imidazoles is dissolved in solvent A, and potassium carbonate is added after being completely dissolved, and reacts 3h or more；
The molecular weight of the polybenzimidazoles is 5000~200000；
The polybenzimidazoles：The molar ratio of potassium carbonate is 1：1~3；
W/v of the polybenzimidazoles, potassium carbonate in solvent A is 1~20%；
The solvent A is dimethyl sulfoxide or DMAC N,N' dimethyl acetamide；
(2) synthesis of non-ionic side chain modification polybenzimidazole polymer：By being added to for the bromine monomer containing hydroxyl
It is diluted in a certain amount of solvent A, obtains dilution；Dilution every four hours is primary, and 1~2ml is added to step every time
(1) in reaction solution, in 50~80 DEG C of reaction 12h or more after adding；
The bromine monomer structure containing hydroxyl is as follows：
The wherein positive integer that n is 2~10；
The polybenzimidazoles：The molar ratio of bromine monomer containing hydroxyl is not more than 3；
The w/v of the bromine monomer in solvent A containing hydroxyl is 1~15%；
(3) preparation of non-ionic side chain modification polybenzimidazole membrane：The reaction solution that step (2) obtains is poured into precipitating
In agent B, filtering is soaked in 12h in deionized water after washing again, is filtered, washed, dries；Product is dissolved in solvent C again and being matched
At casting film after casting solution, film is soaked in 24~48h in 1mol/L sulfuric acid solution, is impregnated in deionized water by film surface
Extra acid is removed, and non-ionic side chain modification polybenzimidazole membrane can be obtained；
The solvent C is one of dimethyl sulfoxide, DMAC N,N' dimethyl acetamide；
The precipitating reagent B is acetone, one of ethyl acetate；
The casting solution w/v is 2.5~10%.
The washing times of the non-ionic side chain modification polybenzimidazole polymer are more than three times；It is vacuum drying
Temperature is 40~100 DEG C, and the time is 8 hours or more.
The drying temperature of casting method film forming is 50~80 DEG C, and the time is 24~48 hours.
Beneficial effects of the present invention：
(1) a series of non-ionic side chain of differences is synthesized by the non-ionic side chain of grafting different content and modifies polyphenyl simultaneously
Imidazoles can control the water absorption and swelling and other correlated performances of the film prepared.
(2) non-ionic side chain modification polybenzimidazoles has good dissolubility, and solvent selection range is wide, operation
It is simple and quick.
(3) non-ionic side chain modification polybenzimidazoles reaction step is few, and mild condition, can be by changing nonionic
The content of type side chain changes the degree of substitution of film, and the nonionic of polymer lateral chain makes film will not attack master while enhancing mass transfer
Chain can be used as battery diaphragm and be applied in all-vanadium flow battery to make film have compared with high chemical stability.
Detailed description of the invention
Fig. 1 is the result phenogram of non-ionic side chain modification polybenzimidazole membrane.
Specific embodiment
Further detailed description done to the present invention below in conjunction with case study on implementation, but embodiments of the present invention and not only
It is limited to this.
Embodiment 1
The synthesis of non-ionic side chain modification polybenzimidazoles：Under nitrogen protection, by 0.5g polybenzimidazoles
In the three-necked flask of (1.25mmol) 100mL, adds 20mL dimethyl sulfoxide and is made into mixed solution, be gradually warming up to 80 DEG C,
Then the constant 3h or more of temperature is kept, 0.3455g (2mmol) carbonic acid nak response 3h or more is subsequently added into.By 339 μ L
(3.75mmol) bromopropyl alcohol, which is added in 5ml dimethyl sulfoxide solvent, to be diluted, and 1ml dilution is added dropwise every 4h, complete
After adding entirely, then in 80 DEG C of reaction 12h~for 24 hours.
The preparation of non-ionic side chain modification polybenzimidazole membrane：It is above-mentioned that product is precipitated with acetone after reaction, instead
After backwashing wash after by polymer bubble in deionized water 12h or more, during which repeatedly change water, then wash drying again, can be obtained
Non-ionic side chain modifies polybenzimidazoles.It weighs the non-ionic side chain modification polybenzimidazoles of 0.14g and is dissolved in 4.3mL
It in DMSO, is cast in glass mold after casting solution is centrifuged, 60 DEG C of dry 36h obtain polymer film.By polymer film in room
It is soaked under temperature in the sulfuric acid solution of 1mol/L for 24 hours, is then cleaned, impregnated for 24 hours to neutrality repeatedly with deionized water, can be obtained
Non-ionic side chain modifies polybenzimidazole membrane.
The structure of the obtained non-ionic film of this example is as follows：
Test indicate that non-ionic side chain modification polybenzimidazole membrane prepared in the present embodiment is in 80mAcm-2
The coulombic efficiency of lower battery is 97.89%, and energy efficiency 86.24%, voltage efficiency 88.81%, film shows more excellent
The performance of good battery.
Embodiment 2
The synthesis of non-ionic side chain modification polybenzimidazoles：Under nitrogen protection, by 0.5g polybenzimidazoles
In the three-necked flask of (1.25mmol) 100mL, adds 20mL dimethyl sulfoxide and is made into mixed solution, be gradually warming up to 80 DEG C,
Then the constant 3h or more of temperature is kept, 0.3455g (2.5mmol) carbonic acid nak response 3h or more is subsequently added into.By 113 μ L
(1.25mmol) bromopropyl alcohol, which is added in 5ml dimethyl sulfoxide solvent, to be diluted, and 1ml dilution is added dropwise every 4h, complete
After adding entirely, then in 80 DEG C of reaction 12h~for 24 hours.
The preparation of non-ionic side chain modification polybenzimidazole membrane：With case 1
The structure of the obtained non-ionic film of this example is as follows：
Test indicate that non-ionic side chain modification polybenzimidazole membrane prepared in the present embodiment is in 80mAcm-2
The coulombic efficiency of lower battery is 98.7%, and energy efficiency 80.01%, voltage efficiency 81.06%, film shows more excellent
The performance of battery.
Embodiment 3
The synthesis of non-ionic side chain modification polybenzimidazoles：Under nitrogen protection, by 0.5g polybenzimidazoles
In the three-necked flask of (1.25mmol) 100mL, adds 20mL dimethyl sulfoxide and is made into mixed solution, be gradually warming up to 80 DEG C,
Then the constant 3h or more of temperature is kept, 0.3455g (2.5mmol) carbonic acid nak response 3h or more is subsequently added into.By 169.5 μ L
(1.875mmol) bromopropyl alcohol, which is added in 5ml dimethyl sulfoxide solvent, to be diluted, and 1ml dilution is added dropwise every 4h, complete
After adding entirely, then in 80 DEG C of reaction 12h~for 24 hours.
The preparation of non-ionic side chain modification polybenzimidazole membrane：With case 1
The structure of the obtained non-ionic film of this example is as follows：
Test indicate that non-ionic side chain modification polybenzimidazole membrane prepared in the present embodiment is in 80mAcm-2
The coulombic efficiency of lower battery is 97.1%, and energy efficiency 81.42%, voltage efficiency 83.85%, film shows more excellent
The performance of battery.
Embodiment 4
The synthesis of non-ionic side chain modification polybenzimidazoles：Under nitrogen protection, by 0.5g polybenzimidazoles
In the three-necked flask of (1.25mmol) 100mL, adds 20mL dimethyl sulfoxide and is made into mixed solution, be gradually warming up to 80 DEG C,
Then the constant 3h or more of temperature is kept, 0.3455g (2.5mmol) carbonic acid nak response 3h or more is subsequently added into.By 245.3 μ L
(1.875mmol) bromobutanol, which is added in 5ml dimethyl sulfoxide solvent, to be diluted, and 1ml dilution is added dropwise every 4h, complete
After adding entirely, then in 80 DEG C of reaction 12h~for 24 hours.
The preparation of non-ionic side chain modification polybenzimidazole membrane：With case 1
The structure of the obtained non-ionic film of this example is as follows：
Test indicate that non-ionic side chain modification polybenzimidazole membrane prepared in the present embodiment is in 80mAcm-2
The coulombic efficiency of lower battery is 98.23%, and energy efficiency 84.43%, voltage efficiency 85.95%, film shows more excellent
The performance of different battery.
Embodiment 5
The synthesis of non-ionic side chain modification polybenzimidazoles：Under nitrogen protection, by 0.5g polybenzimidazoles
In the three-necked flask of (1.25mmol) 100mL, adds 20mL dimethyl sulfoxide and is made into mixed solution, be gradually warming up to 80 DEG C,
Then the constant 3h or more of temperature is kept, 0.3455g (2.5mmol) carbonic acid nak response 3h or more is subsequently added into.By 490.6 μ L
(2.5mmol) bromobutanol, which is added in 5ml dimethyl sulfoxide solvent, to be diluted, and 1ml dilution is added dropwise every 4h, completely
After adding, then in 80 DEG C of reaction 12h~for 24 hours.
The preparation of non-ionic side chain modification polybenzimidazole membrane：With case 1
The structure of the obtained non-ionic film of this example is as follows：
Test indicate that non-ionic side chain modification polybenzimidazole membrane prepared in the present embodiment is in 80mAcm-2
The coulombic efficiency of lower battery is 96.73%, and energy efficiency 85.13%, voltage efficiency 88.01%, film shows more excellent
The performance of different battery.
Claims (10)
1. a kind of non-ionic side chain modifies polybenzimidazole membrane, which is characterized in that the non-ionic side chain modifies polyphenyl
And the structural formula of imidazoles film is as follows：
Wherein, x=0~1；Y=0~1；The positive integer that n is 2~10.
2. a kind of preparation method of non-ionic side chain modification polybenzimidazole membrane, which is characterized in that steps are as follows：
(1) dissolution of polybenzimidazole polymer：Under inert gas protection, by polybenzimidazoles in 50~80 DEG C of oil bath pan
It is dissolved in solvent A, potassium carbonate is added after being completely dissolved, react 3h or more；
The polybenzimidazoles：The molar ratio of potassium carbonate is 1：1~3；
W/v of the polybenzimidazoles, potassium carbonate in solvent A is 1~20%；
The solvent A is dimethyl sulfoxide or DMAC N,N' dimethyl acetamide；
(2) synthesis of non-ionic side chain modification polybenzimidazole polymer：Being added to for bromine monomer containing hydroxyl is certain
It is diluted in the solvent A of amount, obtains dilution；Dilution every four hours is primary, and 1~2ml is added to step (1) every time
In reaction solution, in 50~80 DEG C of reaction 12h or more after adding；
The bromine monomer structure containing hydroxyl is as follows：
The wherein positive integer that n is 2~10；
The polybenzimidazoles：The molar ratio of bromine monomer containing hydroxyl is not more than 3；
The w/v of the bromine monomer in solvent A containing hydroxyl is 1~15%；
(3) preparation of non-ionic side chain modification polybenzimidazole membrane：The reaction solution that step (2) obtains is poured into precipitating reagent B
In, filtering is soaked in 12h in deionized water after washing again, is filtered, washed, dries；Product is dissolved in solvent C again and being made into
Film is soaked in 24~48h in 1mol/L sulfuric acid solution, impregnated in deionized water film surface is more by casting film after casting solution
Remaining acid, which is removed, modifies polybenzimidazole membrane to get non-ionic side chain；
The solvent C is one of dimethyl sulfoxide, DMAC N,N' dimethyl acetamide；
The precipitating reagent B is acetone, one of ethyl acetate；
The casting solution w/v is 2.5~10%.
3. preparation method according to claim 2, which is characterized in that the molecular weight of the polybenzimidazoles be 5000~
200000。
4. preparation method according to claim 2 or 3, which is characterized in that the non-ionic side chain modification polyphenyl is simultaneously
The washing times of imidazoles polymer are more than three times.
5. preparation method according to claim 2 or 3, which is characterized in that the drying is vacuum drying, temperature 40
~100 DEG C, the time is 8 hours or more.
6. the preparation method according to claim 4, which is characterized in that the drying be vacuum drying, temperature be 40~
100 DEG C, the time is 8 hours or more.
7. according to preparation method described in claim 2,3 or 6, which is characterized in that casting method film forming drying temperature be 50~
80 DEG C, the time is 24~48 hours.
8. the preparation method according to claim 4, which is characterized in that the drying temperature of casting method film forming is 50~80 DEG C,
Time is 24~48 hours.
9. preparation method according to claim 5, which is characterized in that the drying temperature of casting method film forming is 50~80 DEG C,
Time is 24~48 hours.
10. according to preparation method described in claim 2,3,6,8 or 9, it is characterised in that：After potassium carbonate is added in step (1)
Reaction condition be：Temperature is 30~80 DEG C, and the time is 12 hours or more.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109904370A (en) * | 2019-02-19 | 2019-06-18 | 中国地质大学（武汉） | A kind of porous polybenzimidazole polymer electrolyte membrance and preparation method and application |
| CN114188585A (en) * | 2021-11-26 | 2022-03-15 | 大连理工大学 | Preparation method of ion exchange membrane containing hydrophilic ion screening micropores |
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| CN114188585B (en) * | 2021-11-26 | 2024-02-09 | 大连理工大学 | Preparation method of ion exchange membrane containing hydrophilic ion screening micropores |
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