CN109687003A - A kind of cross-linking type alkaline anionic membrane and preparation method thereof based on piperidines - Google Patents
A kind of cross-linking type alkaline anionic membrane and preparation method thereof based on piperidines Download PDFInfo
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- CN109687003A CN109687003A CN201811440696.4A CN201811440696A CN109687003A CN 109687003 A CN109687003 A CN 109687003A CN 201811440696 A CN201811440696 A CN 201811440696A CN 109687003 A CN109687003 A CN 109687003A
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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
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1067—Polymeric electrolyte materials characterised by their physical properties, e.g. porosity, ionic conductivity or thickness
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- 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
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Abstract
The invention discloses a kind of novel anionic exchange membranes and preparation method thereof, the anion-exchange membrane is by polymer and halopiperidine initial reaction containing halomethyl groups, and with 1, the crosslinking of the binary such as 4- lupetazin is prepared, the benzylic positions of such film piperidines ion excellent using alkaline stability, the chemical stability under alkaline environment are more preferable；Polycation can effectively improve ionic conductivity；In addition, crosslinking can either inhibit to be swollen, and it is able to maintain the flexibility and excellent conductivity of film.Anionic membrane prepared by the present invention shows excellent chemical stability, higher conductivity, low water absorbable and resistance to swelling, is suitble to apply in terms of alkaline fuel cell.
Description
Technical field
The invention belongs to battery field of membrane material, it is related to a kind of cross-linking type alkaline anionic membrane based on piperidines and its preparation
Method.
Background technique
Energy crisis and environmental pollution have become the most important two large problems that today's society is faced, and fuel cell is made
Extensive concern for new cleaning fuel, by countries in the world.Alkaline polymer fuel cell is fast by its kinetics, can
To use non-precious metal catalyst, without carbonate crystallization, fuel permeability be low etc., advantages achieve fast development.
But many challenges, alkaline anion-exchange membrane are also faced on the road of alkaline polymer commercializing fuel cells
As critical material, the big main problem of poor chemical stability two in there are conductivity low, alkaline environment.Therefore, how yin is improved
The chemical stability and conductivity of ionic membrane become urgent problem to be solved.
As traditional ion-exchange group, under the conditions of high-temperature alkali SN occurs for quaternary ammonium2Replace or Hoffman eliminate and
Ylide degradation, in recent years, the dielectric film containing the novel ions base such as imidazoles, morpholine, guanidine radicals, pyrrolidines starts to cause people
Interest.
In contrast, in recent years, Kreuer et al. find 6 yuan of aliphatic heterocyclic group cation piperidines in alkaline condition and
It is shown under high temperature to the resistance of nucleophilic displacement of fluorine and elimination.Author is attributed to piperidine structure in the high transition of degradation reaction
State energy and the strain of low ring, thus more stable under alkaline environment.
Summary of the invention
For two large problems existing for above-mentioned anionic membrane, the present invention propose a kind of novel alkaline fuel cell it is negative from
Two kinds of groups with a conjugated structure are combined and form double resonant type ionization reagent by proton exchange and preparation method thereof, with
Main polymer chain crosslinking, prepares the cross-linking type anionic membrane with dual positive center, such anionic membrane has preferable resistance to
Alkalinity, thermal stability and higher conductivity.
In order to achieve the above object, the technical solution adopted by the present invention is that:
A kind of cross-linking type alkaline anionic membrane based on piperidines, be applied to fuel cell field, the cross-linking type alkalinity yin from
Proton exchange is prepared by the polymer based on halopiperidine containing halomethyl groups with binary cross-linking agents.Described is halogen
The polymer of methyl group is bisphenol-a polysulfone, biphenyl type polysulfones, polyphenylene oxide or polystyrene, the halomethylation journey of polymer
Degree range is 0.1~2mmolg-1.The halopiperidine are as follows:
The chloro- 1- methyl piperidine of 4-1- (2- chloroethyl) piperidine hydrochlorate4- bromine piperidines hydrogen
BromateThe bromo- N-Boc- piperidines of 4-Deng.
A kind of preparation method of the cross-linking type alkaline anionic membrane based on piperidines, the preparation method is first by base containing chloromethyl
The polymer of group reacts to obtain first step product with piperidines containing halogen, then react with excessive binary crosslinking agent again
To cross-linking type anion-exchange membrane.Preparation process includes polymer film main chain chloromethylation, the ionization of polymer film main chain, polymerization
Object film Cross-linked, casting film and alkali process.Specific step is as follows:
(1) polymer film main chain chloromethylation
It dissolves a polymer in solvent A, anhydrous SnCl is separately added under controlled atmosphere4As catalyst, chloromethyl
Octyl Ether is as chloromethylation reagents；Polymer, solvent A, chloromethyl Octyl Ether molar ratio be 1:200~240:9~10；
It is warming up to 30 DEG C of 0.5~2h of reaction.Chloromethylation degree is controlled by the control reaction time, reaction mixture is poured into precipitating
It is precipitated in agent, vacuum drying obtains chloromethylation products.
Step (1) it is described can the polymer of chloromethylation include bisphenol-a polysulfone, biphenyl type polysulfones.
Step (1) described solvent A can be methanol, ethyl alcohol or acetone.The precipitating reagent be ethyl acetate, petroleum ether or
Acetone.
Step (1) the vacuum drying temperature is 40~100 DEG C, and the time is 12~48 hours；
(2) ionization of polymer film main chain
The main polymer chain of chloromethylation is dissolved in organic solvent, ionization reagent is added, at 60~100 DEG C, into
Row ion reaction 12~48 hours, reaction mixture is poured into precipitating reagent and is precipitated, vacuum drying obtains chloromethylation products.
The polymer, organic solvent, ionization reagent molar ratio be 1:10:1.5~2；The binary ionization reagent be containing
Halogen piperidines reagent.
Step (2) described organic solvent can be N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N- methylpyrrole
Alkanone or dimethyl sulfoxide, the precipitating reagent are ethyl acetate, petroleum ether or acetone.
Ionization reagent used in step (2) described ion reaction may is that
The chloro- 1- methyl piperidine of 4-1- (2- chloroethyl) piperidine hydrochlorate4- bromine piperidines hydrogen
BromateThe bromo- N-Boc- piperidines of 4-Deng.
(3) Cross-linked of polymer film
The main polymer chain of step (2) chloromethylation is dissolved in organic solvent, binary cross-linking reagent is added, 80~
At 100 DEG C, carries out Cross-linked and react 168~240 hours.The polymer, organic solvent, Cross-linked reagent molar ratio be
1:10:1~5.
Step (3) described organic solvent can be N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N- methyl pyrrole
Pyrrolidone or dimethyl sulfoxide.
Step (3) Cross-linked, which reacts binary Cross-linked reagent used, may is that
1,4- lupetazin4- piperidinyl piperidine4,4'- trimethylenes are bis- (1- methyl piperidine)Deng.
(4) casting film
Reaction mixture made from step (3) is placed in casting film or casting film-forming on glass plate, 60 DEG C~80 DEG C quiet
It sets 12~36 hours.
(5) alkali process obtains anion-exchange membrane
Film obtained above is removed from glass pane surface, is placed in 1.0M aqueous slkali and impregnates 24~48 hours, wash away film
The free ion in surface obtains cross-linking type anionic membrane.
The invention has the benefit that
(1) high transition state energy and low ring strain of the piperidine structure because of its degradation reaction, to enhance anionic membrane
Alkali resistance；Polycation structure forms high density ion transmission channel and provides conduction ionic group, is obviously improved the conductivity of film；
(2) crosslinking agent is capable of forming and is crosslinked by control additive amount and reaction time and reaction temperature, inhibits swelling, system
The anion-exchange membrane of standby high substituted degree, improves mechanical strength on the basis of guaranteeing conductivity, to alleviate conductivity and machine
Contradiction between tool intensity.
Detailed description of the invention
Fig. 1 is the FT-IR spectrogram and chemical structural formula of 1 cross-linking type amberplex of embodiment.In spectrogram: abscissa is wave
Number, ordinate is intensity.
Specific embodiment
The preparation method for the cross-linking type anionic membrane that present invention be described in more detail by the following examples is related to.
Embodiment 1
At room temperature, the 2g chloromethyl polysulphone that the degree of functionalization of preparation is 100 is taken to be dissolved in n,N-Dimethylformamide,
Obtain homogeneous reaction liquid.The chloro- 1- methyl piperidine of 4- for adding 1.417g thereto, reacts 48 hours at 60 DEG C.Reaction is completed
Afterwards, it is precipitated in ethyl acetate.It is filtered after stirring 24 hours at room temperature.Repeatedly for three times, it is ensured that polymer is sufficiently washed
It washs.
It takes the polymer 0.4g of previous step reaction synthesis to be dissolved in n,N-Dimethylformamide, is taken out after dissolution, centrifuge tube
Interior centrifugation is three times.It takes supernatant liquor 4mL to pour into plastic film mulch bottle, adds 0.072mL1,4- lupetazin reacts at 80 DEG C
240 hours, it is ensured that successfully replace.
By above-mentioned reaction solution casting film on a glass, at 60 DEG C dry 36 hours to get arriving cross-linking type anionic membrane.
By above-mentioned anion-exchange membrane from glass plate get under, immerse 1M NaOH aqueous solution in 24 hours, be replaced as alkalinity
Film.
Water absorption rate is 6.52% to prepared anion-exchange membrane at room temperature, swelling ratio 1.33%, hydroxyl at 25 DEG C
Conductivity is 15.82mS/cm.
Embodiment 2
At room temperature, the 2g chloromethyl polysulphone that the degree of functionalization of preparation is 100 is taken to be dissolved in n,N-Dimethylformamide,
Homogeneous reaction liquid is obtained, 1- (2- chloroethyl) piperidine hydrochlorate of 1.675g is added thereto, is reacted 36 hours at 80 DEG C.
After the reaction was completed, it is precipitated in ethyl acetate.It is filtered after stirring 24 hours at room temperature.Repeatedly for three times, it is ensured that polymerization
Object sufficiently washs.
It takes the polymer 0.4g of previous step reaction synthesis to be dissolved in n,N-Dimethylformamide, is taken out after dissolution, centrifuge tube
Interior centrifugation is three times.It takes supernatant liquor 4mL to pour into plastic film mulch bottle, adds 0.072mL1,4- lupetazin reacts at 90 DEG C
204 hours, it is ensured that successfully replace.
By above-mentioned reaction solution casting film on a glass, at 70 DEG C dry 24 hours to get arriving cross-linking type anionic membrane.
By above-mentioned anion-exchange membrane from glass plate get under, immerse 1M NaOH aqueous solution in 24 hours, be replaced as alkalinity
Film.
Water absorption rate is 6.21% to prepared anion-exchange membrane at room temperature, swelling ratio 2.33%, hydroxyl at 25 DEG C
Conductivity is 24.21mS/cm.
Embodiment 3
At room temperature, the 2g chloromethyl polysulphone that the degree of functionalization of preparation is 90 is taken to be dissolved in n,N-dimethylacetamide,
Homogeneous reaction liquid is obtained, the 4- bromine piperidine hydrobromic acid salt of 1.247g is added thereto, is reacted 12 hours at 100 DEG C.It has reacted
Cheng Hou is precipitated in petroleum ether.It is filtered after stirring 24 hours at room temperature.Repeatedly for three times, it is ensured that polymer is sufficiently washed
It washs.
The polymer 0.4g of previous step reaction synthesis is taken to be dissolved in n,N-dimethylacetamide, centrifugation in centrifuge tube after dissolution
Three times.It takes supernatant liquor 4mL to pour into plastic film mulch bottle, adds 0.045g 4- piperidinyl piperidine, reacted 168 hours at 100 DEG C,
It assures success and replaces.
By above-mentioned reaction solution casting film on a glass, handed at 80 DEG C to get to cross-linking type anion within dry 12 hours
Change film.
Above-mentioned anion-exchange membrane is removed from glass plate, immerses in 1M NaOH aqueous solution 48 hours, is replaced as alkalinity
Film.
Water absorption rate is 6.39% to prepared anion-exchange membrane at room temperature, swelling ratio 2.66%, hydroxyl at 25 DEG C
Conductivity is 20mS/cm.
Embodiment 4
At room temperature, it takes the 2g chloromethyl polysulphone that the degree of functionalization of preparation is 110 to be dissolved in N-Methyl pyrrolidone, obtains
To homogeneous reaction liquid, the 4- bromine piperidine hydrobromic acid salt of 1.247g is added thereto, is reacted 48 hours at 80 DEG C.Reaction is completed
Afterwards, it is poured slowly into petroleum ether and is precipitated.It is filtered after stirring 24 hours at room temperature.Repeatedly for three times, it is ensured that polymer fills
Divide washing.
It takes the polymer 0.4g of previous step reaction synthesis to be dissolved in N-Methyl pyrrolidone, is taken out after dissolution, in centrifuge tube
Centrifugation is three times.Supernatant liquor 4mL is taken to pour into plastic film mulch bottle, 4, the 4'- trimethylene for adding 0.084g is bis- (1- methyl piperidine),
It is reacted 240 hours at 80 DEG C, it is ensured that successfully replace.
By above-mentioned reaction solution casting film on a glass, at 60 DEG C dry 36 hours to get arriving cross-linking type anionic membrane.
By above-mentioned anion-exchange membrane from glass plate get under, immerse 1M NaOH aqueous solution in 48 hours, be replaced as alkalinity
Film.
Water absorption rate is 12.37% to prepared anion-exchange membrane at room temperature, swelling ratio 2.32%, hydroxyl at 25 DEG C
Conductivity is 25.54mS/cm.
Embodiment 5
At room temperature, it takes the 2g chloromethyl polysulphone that the degree of functionalization of preparation is 100 to be dissolved in dimethyl sulfoxide, obtains
Phase reaction liquid adds the bromo- N-Boc- piperidines of 4- of 1.417g thereto, reacts 48 hours at 60 DEG C.After the reaction was completed, slowly
It pours into acetone and is precipitated.It is filtered after stirring 24 hours at room temperature.Repeatedly for three times, it is ensured that polymer sufficiently washs.
It takes the polymer 0.4g of previous step reaction synthesis to be dissolved in dimethyl sulfoxide, is taken out after dissolution, centrifugation in centrifuge tube
Three times.Supernatant liquor 4mL is taken to pour into plastic film mulch bottle, 4, the 4'- trimethylene for adding 0.084g is bis- (1- methyl piperidine), 80
It is reacted 240 hours at DEG C, it is ensured that successfully replace.
By above-mentioned reaction solution casting film on a glass, at 60 DEG C dry 36 hours to get arriving cross-linking type anionic membrane.
By above-mentioned anion-exchange membrane from glass plate get under, immerse 1M NaOH aqueous solution in 48 hours, be replaced as alkalinity
Film.
Water absorption rate is 7.08% to prepared anion-exchange membrane at room temperature, swelling ratio 1.25%, hydroxyl at 25 DEG C
Conductivity is 10.88mS/cm.
Embodiment described above only expresses embodiments of the present invention, and but it cannot be understood as to the invention patent
Range limitation, it is noted that for those skilled in the art, without departing from the inventive concept of the premise, also
Several modifications and improvements can be made, these are all belonged to the scope of protection of the present invention.
Claims (6)
1. a kind of cross-linking type alkaline anionic membrane based on piperidines, which is characterized in that the cross-linking type alkaline anion-exchange membrane by
Polymer based on halopiperidine containing halomethyl groups is prepared with binary cross-linking agents；It is described containing halomethyl groups
Polymer is bisphenol-a polysulfone, biphenyl type polysulfones, polyphenylene oxide or polystyrene, and the halomethylation extent and scope of polymer is 0.1
~2mmolg-1；The halopiperidine are as follows:
The chloro- 1- methyl piperidine of 4-1- (2- chloroethyl) piperidine hydrochlorate4- bromine piperidines hydrobromic acid
SaltThe bromo- N-Boc- piperidines of 4-
2. a kind of preparation method of the cross-linking type alkaline anionic membrane based on piperidines, it is characterised in that following steps:
(1) polymer film main chain chloromethylation
(2) ionization of polymer film main chain
The main polymer chain of chloromethylation is dissolved in organic solvent, be added ionization reagent, at 60~100 DEG C, carry out from
Sonization is reacted 12~48 hours, and reaction mixture is poured into precipitating reagent and is precipitated, and vacuum drying obtains chloromethylation products；It is described
Polymer, organic solvent, ionization reagent molar ratio be 1:10:1.5~2；The binary ionization reagent is containing halogen
Piperidines reagent；
(3) Cross-linked of polymer film
The main polymer chain of step (2) chloromethylation is dissolved in organic solvent, binary cross-linking reagent is added, at 80~100 DEG C
Under, it carries out Cross-linked and reacts 168~240 hours；The polymer, organic solvent, Cross-linked reagent molar ratio be 1:10:
1~5；
The Cross-linked reacts binary Cross-linked reagent used
1,4- lupetazin4- piperidinyl piperidine4,4'- trimethylenes are bis- (1- methyl piperidine)Deng；
(4) casting film
Reaction mixture made from step (3) is placed in casting film or casting film-forming on glass plate, 60 DEG C~80 DEG C stand 12
~36 hours；
(5) alkali process obtains anion-exchange membrane
Film obtained above is removed from glass pane surface, is placed in 1.0M aqueous slkali and impregnates 24~48 hours, wash away film surface
Free ion obtains cross-linking type anionic membrane.
3. preparation method according to claim 2, which is characterized in that polymer film main chain chloromethane in the step (1)
Base the following steps are included:
It dissolves a polymer in solvent, anhydrous SnCl is separately added under controlled atmosphere4As catalyst, chloromethyl Octyl Ether
As chloromethylation reagents；Polymer, solvent A, chloromethyl Octyl Ether molar ratio be 1:200~240:9~10；It is warming up to 30
DEG C reaction 0.5~2h；Chloromethylation degree is controlled by the control reaction time, reaction mixture is poured into precipitating reagent and is sunk
It forms sediment, vacuum drying obtains chloromethylation products.
4. preparation method according to claim 2 or 3, which is characterized in that ion reaction described in step (2) it is used from
Sonization reagent includes:
The chloro- 1- methyl piperidine of 4-1- (2- chloroethyl) piperidine hydrochlorate4- bromine piperidines hydrobromic acid
SaltThe bromo- N-Boc- piperidines of 4-
5. preparation method according to claim 2 or 3, which is characterized in that step (2) described organic solvent can be N, N-
Dimethylformamide, n,N-dimethylacetamide, N-Methyl pyrrolidone or dimethyl sulfoxide, the precipitating reagent are acetic acid second
Ester, petroleum ether or acetone；Step (3) described organic solvent can be N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N-
Methyl pyrrolidone or dimethyl sulfoxide.
6. the preparation method according to claim 4, which is characterized in that step (2) described organic solvent can be N, N- bis-
Methylformamide, n,N-dimethylacetamide, N-Methyl pyrrolidone or dimethyl sulfoxide, the precipitating reagent are acetic acid second
Ester, petroleum ether or acetone；Step (3) described organic solvent can be N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N-
Methyl pyrrolidone or dimethyl sulfoxide.
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Cited By (6)
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| CN110690486A (en) * | 2019-11-07 | 2020-01-14 | 大连理工大学 | Preparation method of crosslinking type alkaline anionic membrane based on flexible long-side-chain multi-cation structure |
| CN110690487A (en) * | 2019-11-07 | 2020-01-14 | 大连理工大学 | Preparation method of basic anion membrane based on branched anaerobic main chain |
| CN111725549A (en) * | 2020-06-24 | 2020-09-29 | 常州大学 | Polymer electrolyte membrane based on polyvinyl alcohol and preparation method thereof |
| CN112143005A (en) * | 2020-09-21 | 2020-12-29 | 浙江工业大学 | Preparation and application of piperidine crosslinking type bromomethylated polyphenylene oxide anion exchange membrane with acid blocking function |
| CN112759778A (en) * | 2020-12-28 | 2021-05-07 | 武汉大学 | High-strength alkaline anionic polymer crosslinked membrane and preparation method thereof |
| CN114144453A (en) * | 2019-07-22 | 2022-03-04 | 赢创运营有限公司 | Polymeric anion conducting membranes |
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| CN114144453A (en) * | 2019-07-22 | 2022-03-04 | 赢创运营有限公司 | Polymeric anion conducting membranes |
| CN110690486A (en) * | 2019-11-07 | 2020-01-14 | 大连理工大学 | Preparation method of crosslinking type alkaline anionic membrane based on flexible long-side-chain multi-cation structure |
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| CN111725549A (en) * | 2020-06-24 | 2020-09-29 | 常州大学 | Polymer electrolyte membrane based on polyvinyl alcohol and preparation method thereof |
| CN111725549B (en) * | 2020-06-24 | 2021-05-25 | 常州大学 | Polymer electrolyte membrane based on polyvinyl alcohol and preparation method thereof |
| CN112143005A (en) * | 2020-09-21 | 2020-12-29 | 浙江工业大学 | Preparation and application of piperidine crosslinking type bromomethylated polyphenylene oxide anion exchange membrane with acid blocking function |
| CN112759778A (en) * | 2020-12-28 | 2021-05-07 | 武汉大学 | High-strength alkaline anionic polymer crosslinked membrane and preparation method thereof |
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Application publication date: 20190426 |