CN104538657B - A kind of cross-linked chitosan/nitrogenous phosphonic acids based polysiloxane high temperature proton exchange film and preparation method thereof - Google Patents

A kind of cross-linked chitosan/nitrogenous phosphonic acids based polysiloxane high temperature proton exchange film and preparation method thereof Download PDF

Info

Publication number
CN104538657B
CN104538657B CN201410785191.7A CN201410785191A CN104538657B CN 104538657 B CN104538657 B CN 104538657B CN 201410785191 A CN201410785191 A CN 201410785191A CN 104538657 B CN104538657 B CN 104538657B
Authority
CN
China
Prior art keywords
chitosan
solution
high temperature
proton exchange
cross
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN201410785191.7A
Other languages
Chinese (zh)
Other versions
CN104538657A (en
Inventor
高山俊
尹珊珊
沈春晖
李伟
李慧琳
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wuhan University of Technology WUT
Original Assignee
Wuhan University of Technology WUT
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wuhan University of Technology WUT filed Critical Wuhan University of Technology WUT
Priority to CN201410785191.7A priority Critical patent/CN104538657B/en
Publication of CN104538657A publication Critical patent/CN104538657A/en
Application granted granted Critical
Publication of CN104538657B publication Critical patent/CN104538657B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
    • H01M8/028—Sealing means characterised by their material
    • H01M8/0284—Organic resins; Organic polymers
    • 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
    • H01M8/02—Details
    • H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
    • H01M8/0286—Processes for forming seals
    • 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
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/1233—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte with one of the reactants being liquid, solid or liquid-charged
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Fuel Cell (AREA)
  • Conductive Materials (AREA)

Abstract

The present invention relates to a kind of cross-linked chitosan/nitrogenous phosphonic acids based polysiloxane high temperature proton exchange film and preparation method thereof, it is to use following steps products therefrom：1) chitosan solution is prepared；2) solution containing nitrogen organic phosphonic acid is prepared；3) nitrogen organic phosphonic acid solution will be contained to be slowly dropped in chitosan solution, stirred, then amino silicone will be slowly dropped in the mixed solution, and obtain sol solutionses；4) the aldehyde crosslinking agent aqueous solution is slowly added into sol solutionses, is uniformly mixing to obtain coagulant liquid；5) coagulant liquid is poured into polytetrafluoroethylene (PTFE) mould, room temperature is aged 2~3 days after 80 DEG C of drying, and then it is peeled off from polytetrafluoroethylene (PTFE) mould with being heat-treated 2h respectively under the conditions of 150 DEG C, after cooling in 100 DEG C, 120 DEG C successively and is obtained.Preparation process of the present invention is simple, and reaction condition is gentle, and the PEM prepared still has higher proton conductivity, and good thermal stability under high temperature, anhydrous condition.

Description

A kind of cross-linked chitosan/nitrogenous phosphonic acids based polysiloxane high temperature proton exchange film and its Preparation method
Technical field
The invention belongs to field of fuel cell technology, it is related to a kind of cross-linked chitosan/nitrogenous phosphonic acids based polysiloxane high temperature PEM and preparation method thereof.
Background technology
Proton Exchange Membrane Fuel Cells (PEMFC) is fuel cell system of the class using PEM as electrolyte, This fuel cell is also frequently referred to as solid polymer fuel cells.And PEM is the core component of fuel cell, It directly affects battery performance and life-span.PEM for PEMFC is needed with high H+Conducting power, in addition it is also necessary to There is good proton conductivity and certain mechanical strength under high temperature low humidity condition of work.
Conventional proton exchange membrane material has perfluorinated sulfonic acid polymer, PAEK, polyether-ether-ketone, chitosan and gathered at present The polymer such as acid amides.The research of the wherein PEM based on chitosan has obtained increasing concern, because shell Glycan is widely present in crab shell and shrimp shell, is the product of chitin deacetylase base, with low toxicity, biocompatibility, degradable Property the advantages of, chitosan film-forming process is simple, and cost is low.In addition, the cyclic structure in chitosan molecule ensure that chitosan film Thermo-chemical stability, and enough mechanical properties.There is hydroxyl and amino on chitosan monomer, show that chitosan film has It is prepared into the potentiality of high-performance proton membrane.But, research shows the matter of non-crosslinked and modified chitosan dry film at room temperature Sub- conductivity is only 10-9S·cm-1, equivalent to insulating materials.This can not meet the requirement to PEM electrical conductivity completely, Therefore processing is modified to natural chitosan film to be very important.
In the modification to chitosan, phosphine (phosphorus) acid cross-linked chitosan is a kind of method for improving electrical conductivity.Phosphine (phosphorus) acid It is a kind of both sexes acid, is both proton acceptor and proton donor.Phosphine (phosphorus) acid degree of dissociation under liquid environment is up to 7.4%, body There is substantial amounts of H in system+, its diffusion rate can reach 2 × 10-5cm2/ s, is a kind of ideal proton carrier.In liquid In state phosphine (phosphorus) acid system, hydrogen bond is mainly formed at H3PO4/H2PO4 -Or H4PO4 +/H3P04Between, pass through intermolecular dynamic hydrogen bond Formation and fracture, make proton in intermolecular jump, so as to complete the transmission of proton.
At present, the sour crosslinked chitosan film of phosphine (phosphorus) has obtained certain achievement in research.Cui et al. using chitosan (CS) with Phosphotungstic acid is prepared for new proton conductive membrane, prepared film is homogeneous, stably, without obvious phenomenon of phase separation, at 210 DEG C Lower excellent heat stability, at 80 DEG C, electrical conductivity is up to 0.024Scm-1.But with the rise of temperature, phosphotungstic acid gathers with shell Ionomer declines between sugar, understand some phosphotungstic acid and leak, thus cause electrical conductivity decline (Cui Z, Liu C,Lu T,etal.Polyelectrolyte complexes of chitosan and phosphotungstic acid as proton-conducting membranes for direct methanol fuel cells[J].Journal of Power Sources,2007,167(1):94-99.)。
The content of the invention
The technical problems to be solved by the invention are that there is provided one kind crosslinking shell for above shortcomings in the prior art Glycan/nitrogenous phosphonic acids based polysiloxane high temperature proton exchange film and preparation method thereof, this method preparation process is simple, reaction condition Gently, and the PEM for preparing still has higher proton conductivity, and heat endurance under high temperature, anhydrous condition Well.
In order to solve the above technical problems, the technical scheme that the present invention is provided is：
A kind of cross-linked chitosan/nitrogenous phosphonic acids based polysiloxane high temperature proton exchange film is provided, it is to use following steps Products therefrom：
1) under normal temperature, Chitosan powder is dissolved in aqueous acetic acid, is sufficiently stirred for being uniformly dissolved it, shell is obtained and gathers Sugar juice；
2) nitrogen organic phosphonic acid will be contained to be dissolved in deionized water, lasting stirring at room temperature obtains concentration for 0.17~1.50mol/ L solution containing nitrogen organic phosphonic acid；
3) at room temperature by step 2) gained solution containing nitrogen organic phosphonic acid is slowly dropped to step 1) obtained by chitosan solution, Stir and obtain mixed solution, wherein solution containing nitrogen organic phosphonic acid is 1 with chitosan solution volume ratio：1~2：1, then Amino silicone is slowly dropped in the mixed solution, wherein in amino silicone and the solution containing nitrogen organic phosphonic acid Silicon, P elements mol ratio are 4:1~4:7, stir, obtain sol solutionses；
4) the aldehyde crosslinking agent aqueous solution is slowly added into step 3) in gained sol solutionses, the wherein aldehyde crosslinking agent aqueous solution Volume ratio with sol solutionses is 1：10~1：20, it is uniformly mixing to obtain coagulant liquid；
5) by step 4) gained coagulant liquid pour into polytetrafluoroethylene (PTFE) mould, room temperature be aged 2~3 days after 80 DEG C dry, Then successively in 100 DEG C, 120 DEG C with being heat-treated 2~4h respectively under the conditions of 150 DEG C, by it from polytetrafluoroethylene (PTFE) mould after cooling Upper stripping obtains cross-linked chitosan/nitrogenous phosphonic acids based polysiloxane high temperature proton exchange film.
By such scheme, step 1) the chitosan molecule amount be 5~70,000, deacetylation>85%, the acetic acid is water-soluble Liquid volumetric concentration is 1~2%, and the chitosan solution mass concentration is 1~2%.
By such scheme, step 2) it is described containing nitrogen organic phosphonic acid be ATMP (ATMP), ethylenediamine tetraacetic methene One kind in phosphonic acids (EDTMP), hexapotassium (HDTMP).
By such scheme, step 3) amino silicone be 3- aminopropyl triethoxysilanes (APTES) or 3- amino One kind in propyl trimethoxy silicane (APTMS).
By such scheme, step 4) aldehyde crosslinking agent is one kind in glutaraldehyde or glyoxal, aldehyde crosslinking agent water Liquor capacity concentration is 1~5%.
The preparation method step of cross-linked chitosan of the present invention/nitrogenous phosphonic acids based polysiloxane high temperature proton exchange film is as follows：
1) under normal temperature, Chitosan powder is dissolved in aqueous acetic acid, is sufficiently stirred for being uniformly dissolved it, shell is obtained and gathers Sugar juice；
2) nitrogen organic phosphonic acid will be contained to be dissolved in deionized water, lasting stirring at room temperature obtains concentration for 0.17~1.50mol/ L solution containing nitrogen organic phosphonic acid；
3) at room temperature by step 2) gained solution containing nitrogen organic phosphonic acid is slowly dropped to step 1) obtained by chitosan solution, Stir and obtain mixed solution, wherein solution containing nitrogen organic phosphonic acid is 1 with chitosan solution volume ratio：1~2：1, then Amino silicone is slowly dropped in the mixed solution, wherein in amino silicone and the solution containing nitrogen organic phosphonic acid Silicon, P elements mol ratio are 4:1~4:7, stir, obtain sol solutionses；
4) the aldehyde crosslinking agent aqueous solution is slowly added into step 3) in gained sol solutionses, the wherein aldehyde crosslinking agent aqueous solution Volume ratio with sol solutionses is 1：10~1：20, it is uniformly mixing to obtain coagulant liquid；
5) by step 4) gained coagulant liquid pour into polytetrafluoroethylene (PTFE) mould, room temperature be aged 2~3 days after 80 DEG C dry, Then successively in 100 DEG C, 120 DEG C with being heat-treated 2~4h respectively under the conditions of 150 DEG C, by it from polytetrafluoroethylene (PTFE) mould after cooling Upper stripping obtains cross-linked chitosan/nitrogenous phosphonic acids based polysiloxane high temperature proton exchange film.
By such scheme, step 1) the chitosan molecule amount be 5~70,000, deacetylation>85%, the acetic acid is water-soluble Liquid volumetric concentration is 1~2%, and the chitosan solution mass concentration is 1~2%.
By such scheme, step 2) it is described containing nitrogen organic phosphonic acid be ATMP, ethylene diamine tetra methylene phosphonic acid, oneself One kind in the methylenephosphonic acid of diamines four.
By such scheme, step 3) amino silicone be 3- aminopropyl triethoxysilanes or 3- aminopropyl front threes One kind in TMOS.
By such scheme, step 4) aldehyde crosslinking agent is one kind in glutaraldehyde or glyoxal, aldehyde crosslinking agent water Liquor capacity concentration is 1~5%.
The principle of the present invention is：The present invention is using poly- to shell containing nitrogen organic phosphonic acid, amino silicone and aldehyde crosslinking agent Sugar is modified, and the amino on amino and amino silicone on chitosan can be with forming ionomer knot containing nitrogen organic phosphonic acid Structure, it is ensured that the system has preferable filming performance.In addition,-the OH on chitosan can shape with the Si-O keys on amino silicone Into Si-O-Si structures so that the swellbility of film has obtained good control, the pliability without influenceing film.Chitosan and ammonia The phosphine oxygen key on amino, hydroxyl, with organic polyphosphonic on radical siloxane, between phosphine hydroxyl bond hydrogen bond network can be formed, be The conduction of proton provides passage.And aldehyde crosslinking agent cross-linked chitosan is used, schiff bases structure is formed, increases the mechanics of film Performance reduces the swellbility of film simultaneously.
The beneficial effects of the present invention are：1st, film-forming process of the present invention is simple, with low cost, and reaction condition is gentle, and Harmful substance is not produced in preparation process, industrialized mass production is easily realized；2nd, contain in PEM prepared by the present invention Nitrogen organic phosphonic acid can form ionomer structure with chitosan and amino silicone, and produce hydrogen bond action, and the system Nitrogen, phosphine oxygen, phosphine hydroxyl and hydroxyl between can form hydrogen bond network, this causes prepared PEM even in high temperature Also there is higher electrical conductivity under low humidity conditions；3rd, the present invention uses glutaraldehyde or glyoxal cross-linked chitosan, forms schiff bases knot Structure, adds the mechanical property and thermal stability of PEM so that film can be used for a long time under the conditions of 200 DEG C.
Embodiment
To make those skilled in the art more fully understand technical scheme, the present invention is made with reference to embodiment It is described in further detail.
Chitosan powder molecular weight used in the embodiment of the present invention is 7~90,000, deacetylation>85%.
Embodiment 1
A kind of preparation method of cross-linked chitosan/nitrogenous phosphonic acids based polysiloxane high temperature proton exchange film, specific steps are such as Under：
1) under normal temperature, the aqueous acetic acid that 10mL volumetric concentrations are 1% is prepared, 0.1g Chitosan powders are dissolved in acetic acid In the aqueous solution, it is sufficiently stirred for being uniformly dissolved it, obtains chitosan solution；
2) 0.4984g ATMPs are dissolved in 10mL deionized waters, persistently stirring 12h obtains nitrogenous at room temperature Organic phospho acid solution；
3) above-mentioned solution containing nitrogen organic phosphonic acid is slowly dropped in above-mentioned chitosan solution at room temperature, persistently stirred at room temperature Mix 12h and obtain mixed solution, then 4.4274g amino silicones (3- aminopropyl triethoxysilanes) are slowly dropped to described mix Close in solution, wherein amino silicone and silicon, P elements mol ratio in the solution containing nitrogen organic phosphonic acid are 4:1, at room temperature 24h is persistently stirred, sol solutionses are obtained；
4) 1mL volumetric concentrations are slowly added into step 3 for 1% glyoxal solution) obtained by sol solutionses in, stirring 1 ~2h obtains coagulant liquid；
5) by step 4) obtained coagulant liquid poured into polytetrafluoroethylene (PTFE) mould, and 2~3 days are aged at room temperature after 80 DEG C Baking oven in dry 1~2 day, then 2~4h is separately dried with 150 DEG C in 100 DEG C, 120 DEG C successively, by film from poly- four after cooling Taken off in PVF mould, you can obtain cross-linked chitosan/nitrogenous phosphonic acids based polysiloxane high temperature proton exchange film.
Tested through electrochemical workstation, the cross-linked chitosan made by the present embodiment/nitrogenous phosphonic acids based polysiloxane high temperature Silicon P elements mol ratio is 4 in PEM:1, it is that test proton conductivity is under the conditions of 20% in 120 DEG C, relative humidity 0.071S/cm, ion exchange capacity is 0.65mg/mol, and tensile strength is 32.2Mpa, and linear swelling coefficient is 5.24%, is inhaled Water rate is 37.6%, and stability in use is good at 210 DEG C.
Embodiment 2
A kind of preparation method of cross-linked chitosan/nitrogenous phosphonic acids based polysiloxane high temperature proton exchange film, specific steps are such as Under：
1) under normal temperature, the aqueous acetic acid that 10mL volumetric concentrations are 2% is prepared, 0.2g Chitosan powders are dissolved in acetic acid In the aqueous solution, it is sufficiently stirred for being uniformly dissolved it, obtains chitosan solution；
2) 0.9968g ATMPs are dissolved in 10mL deionized waters, persistently stirring 12h obtains nitrogenous at room temperature Organic phospho acid solution；
3) above-mentioned solution containing nitrogen organic phosphonic acid is slowly dropped in above-mentioned chitosan solution at room temperature, persistently stirred at room temperature Mix 12h and obtain mixed solution, then 3.5858g amino silicones (3- TSL 8330s) are slowly dropped to described In mixed solution, wherein amino silicone and silicon, P elements mol ratio in the solution containing nitrogen organic phosphonic acid are 4:2, in room temperature 24h is persistently stirred down, sol solutionses are obtained；
4) 1mL volumetric concentrations are slowly added into step 3 for 2% glutaraldehyde solution) obtained by sol solutionses in, stirring 1 ~2h obtains coagulant liquid；
5) by step 4) obtained coagulant liquid poured into polytetrafluoroethylene (PTFE) mould, and 2~3 days are aged at room temperature after 80 DEG C Baking oven in dry 1~2 day, then 2~4h is separately dried with 150 DEG C in 100 DEG C, 120 DEG C successively, by film from poly- four after cooling Taken off in PVF mould, you can obtain cross-linked chitosan/nitrogenous phosphonic acids based polysiloxane high temperature proton exchange film.
Using with the same method of testing of embodiment one to cross-linked chitosan/poly- silica of nitrogenous phosphonate group obtained by the present embodiment The material of alkane high temperature proton exchange film is tested, the cross-linked chitosan made by the present embodiment/nitrogenous phosphonic acids based polysiloxane Silicon P elements mol ratio is 4 in high temperature proton exchange film:2, test Proton conducting under the conditions of 120 DEG C, relative humidity is 20% Rate is 0.075S/cm, and ion exchange capacity is 0.69mg/mol, and tensile strength is 35.2Mpa, and linear swelling coefficient is 5.84%, water absorption rate is 35.6%, and stability in use is good at 215 DEG C.
Embodiment 3
A kind of preparation method of cross-linked chitosan/nitrogenous phosphonic acids based polysiloxane high temperature proton exchange film, specific steps are such as Under：
1) under normal temperature, the aqueous acetic acid that 10mL volumetric concentrations are 1% is prepared, 0.1g Chitosan powders are dissolved in acetic acid In the aqueous solution, it is sufficiently stirred for being uniformly dissolved it, obtains chitosan solution；
2) 1.6350g ethylene diamine tetra methylene phosphonic acids are dissolved in 10mL deionized waters, persistently stirring 12h is contained at room temperature Nitrogen organic phosphonic acid solution；
3) above-mentioned solution containing nitrogen organic phosphonic acid is slowly dropped in above-mentioned chitosan solution at room temperature, persistently stirred at room temperature Mix 12h and obtain mixed solution, then 4.4274g amino silicones (3- aminopropyl triethoxysilanes) are slowly dropped to described mix Close in solution, wherein amino silicone and silicon, P elements mol ratio in the solution containing nitrogen organic phosphonic acid are 4:3, at room temperature 24h is persistently stirred, sol solutionses are obtained；
4) 1mL volumetric concentrations are slowly added into step 3 for 3% glyoxal solution) obtained by sol solutionses in, stirring 1 ~2h obtains coagulant liquid；
5) by step 4) obtained coagulant liquid poured into polytetrafluoroethylene (PTFE) mould, and 2~3 days are aged at room temperature after 80 DEG C Baking oven in dry 1~2 day, then 2~4h is separately dried with 150 DEG C in 100 DEG C, 120 DEG C successively, by film from poly- four after cooling Taken off in PVF mould, you can obtain cross-linked chitosan/nitrogenous phosphonic acids based polysiloxane high temperature proton exchange film.
Using with the same method of testing of embodiment one to cross-linked chitosan/poly- silica of nitrogenous phosphonate group obtained by the present embodiment The material of alkane high temperature proton exchange film is tested, the cross-linked chitosan made by the present embodiment/nitrogenous phosphonic acids based polysiloxane Silicon P elements mol ratio is 4 in high temperature proton exchange film:3, test Proton conducting under the conditions of 120 DEG C, relative humidity is 20% Rate is 0.080S/cm, and ion exchange capacity is 0.79mg/mol, and tensile strength is 38.2Mpa, and linear swelling coefficient is 6.84%, water absorption rate is 45.6%, and stability in use is good at 205 DEG C.
Embodiment 4
A kind of preparation method of cross-linked chitosan/nitrogenous phosphonic acids based polysiloxane high temperature proton exchange film, specific steps are such as Under：
1) under normal temperature, the aqueous acetic acid that 5mL volumetric concentrations are 2% is prepared, 0.1g Chitosan powders are dissolved in acetic acid In the aqueous solution, it is sufficiently stirred for being uniformly dissolved it, obtains chitosan solution；
2) 2.1800g ethylene diamine tetra methylene phosphonic acids are dissolved in 5mL deionized waters, persistently stirring 12h is contained at room temperature Nitrogen organic phosphonic acid solution；
3) above-mentioned solution containing nitrogen organic phosphonic acid is slowly dropped in above-mentioned chitosan solution at room temperature, persistently stirred at room temperature Mix 12h and obtain mixed solution, then 3.5858g amino silicones (3- TSL 8330s) are slowly dropped to described In mixed solution, wherein amino silicone and silicon, P elements mol ratio in the solution containing nitrogen organic phosphonic acid are 4:4, in room temperature 24h is persistently stirred down, sol solutionses are obtained；
4) 1mL volumetric concentrations are slowly added into step 3 for 5% glutaraldehyde solution) obtained by sol solutionses in, stirring 1 ~2h obtains coagulant liquid；
5) by step 4) obtained coagulant liquid poured into polytetrafluoroethylene (PTFE) mould, and 2~3 days are aged at room temperature after 80 DEG C Baking oven in dry 1~2 day, then 2~4h is separately dried with 150 DEG C in 100 DEG C, 120 DEG C successively, by film from poly- four after cooling Taken off in PVF mould, you can obtain cross-linked chitosan/nitrogenous phosphonic acids based polysiloxane high temperature proton exchange film.
Using with the same method of testing of embodiment one to cross-linked chitosan/poly- silica of nitrogenous phosphonate group obtained by the present embodiment The material of alkane high temperature proton exchange film is tested, the cross-linked chitosan made by the present embodiment/nitrogenous phosphonic acids based polysiloxane Silicon P elements mol ratio is 4 in high temperature proton exchange film:4, test Proton conducting under the conditions of 120 DEG C, relative humidity is 20% Rate is 0.079S/cm, and ion exchange capacity is 0.74mg/mol, and tensile strength is 40.2Mpa, and linear swelling coefficient is 7.84%, water absorption rate is 48.6%, and stability in use is good at 225 DEG C.
Embodiment 5
A kind of preparation method of cross-linked chitosan/nitrogenous phosphonic acids based polysiloxane high temperature proton exchange film, specific steps are such as Under：
1) under normal temperature, the aqueous acetic acid that 10mL volumetric concentrations are 1% is prepared, 0.1g Chitosan powders are dissolved in acetic acid In the aqueous solution, it is sufficiently stirred for being uniformly dissolved it, obtains chitosan solution；
2) 3.0769g hexapotassiums are dissolved in 10mL deionized waters, persistently stirring 12h is contained at room temperature Nitrogen organic phosphonic acid solution；
3) above-mentioned solution containing nitrogen organic phosphonic acid is slowly dropped in above-mentioned chitosan solution at room temperature, persistently stirred at room temperature Mix 12h and obtain mixed solution, then 4.4274g amino silicones (3- aminopropyl triethoxysilanes) are slowly dropped to described mix Close in solution, wherein amino silicone and silicon P elements mol ratio in the solution containing nitrogen organic phosphonic acid are 4:5, hold at room temperature Continuous stirring 24h, obtains sol solutionses；
4) 1mL volumetric concentrations are slowly added into step 3 for 5% glyoxal solution) obtained by sol solutionses in, stirring 1 ~2h obtains coagulant liquid；
5) by step 4) obtained coagulant liquid poured into polytetrafluoroethylene (PTFE) mould, and 2~3 days are aged at room temperature after 80 DEG C Baking oven in dry 1~2 day, then 2~4h is separately dried with 150 DEG C in 100 DEG C, 120 DEG C successively, by film from poly- four after cooling Taken off in PVF mould, you can obtain cross-linked chitosan/nitrogenous phosphonic acids based polysiloxane high temperature proton exchange film.
Using with the same method of testing of embodiment one to cross-linked chitosan/poly- silica of nitrogenous phosphonate group obtained by the present embodiment The material of alkane high temperature proton exchange film is tested, the cross-linked chitosan made by the present embodiment/nitrogenous phosphonic acids based polysiloxane Silicon P elements mol ratio is 4 in high temperature proton exchange film:5, test Proton conducting under the conditions of 120 DEG C, relative humidity is 20% Rate is 0.081S/cm, and ion exchange capacity is 0.78mg/mol, and tensile strength is 44.2Mpa, and linear swelling coefficient is 4.84%, water absorption rate is 40.6%, and stability in use is good at 205 DEG C.
Embodiment 6
A kind of preparation method of cross-linked chitosan/nitrogenous phosphonic acids based polysiloxane high temperature proton exchange film, specific steps are such as Under：
1) under normal temperature, the aqueous acetic acid that 5mL volumetric concentrations are 2% is prepared, 0.1g Chitosan powders are dissolved in acetic acid In the aqueous solution, it is sufficiently stirred for being uniformly dissolved it, obtains chitosan solution；
2) 3.6922g hexapotassiums are dissolved in 5mL deionized waters, persistently stirring 12h is contained at room temperature Nitrogen organic phosphonic acid solution；
3) above-mentioned solution containing nitrogen organic phosphonic acid is slowly dropped in above-mentioned chitosan solution at room temperature, persistently stirred at room temperature Mix 12h and obtain mixed solution, then 3.5858g amino silicones (3- TSL 8330s) are slowly dropped to described In mixed solution, wherein amino silicone and silicon P elements mol ratio in the solution containing nitrogen organic phosphonic acid are 4:6, at room temperature 24h is persistently stirred, sol solutionses are obtained；
4) 1mL volumetric concentrations are slowly added into step 3 for 5% glutaraldehyde solution) obtained by sol solutionses in, stirring 1 ~2h obtains coagulant liquid；
5) by step 4) obtained coagulant liquid poured into polytetrafluoroethylene (PTFE) mould, and 2~3 days are aged at room temperature after 80 DEG C Baking oven in dry 1~2 day, then 2~4h is separately dried with 150 DEG C in 100 DEG C, 120 DEG C successively, by film from poly- four after cooling Taken off in PVF mould, you can obtain cross-linked chitosan/nitrogenous phosphonic acids based polysiloxane high temperature proton exchange film.
Using with the same method of testing of embodiment one to cross-linked chitosan/poly- silica of nitrogenous phosphonate group obtained by the present embodiment The material of alkane high temperature proton exchange film is tested, the cross-linked chitosan made by the present embodiment/nitrogenous phosphonic acids based polysiloxane Silicon P elements mol ratio is 4 in high temperature proton exchange film:6, test Proton conducting under the conditions of 120 DEG C, relative humidity is 20% Rate is 0.086S/cm, and ion exchange capacity is 0.84mg/mol, and tensile strength is 45.2Mpa, and linear swelling coefficient is 6.84%, water absorption rate is 47.6%, and stability in use is good at 235 DEG C.
Embodiment 7
A kind of preparation method of cross-linked chitosan/nitrogenous phosphonic acids based polysiloxane high temperature proton exchange film, specific steps are such as Under：
1) under normal temperature, the aqueous acetic acid that 5mL volumetric concentrations are 1% is prepared, 0.1g Chitosan powders are dissolved in acetic acid In the aqueous solution, it is sufficiently stirred for being uniformly dissolved it, obtains chitosan solution；
2) 4.3077g hexapotassiums are dissolved in 10mL deionized waters, persistently stirring 12h is contained at room temperature Nitrogen organic phosphonic acid solution；
3) above-mentioned solution containing nitrogen organic phosphonic acid is slowly dropped in above-mentioned chitosan solution at room temperature, persistently stirred at room temperature Mix 12h and obtain mixed solution, then 4.4274g amino silicones (3- aminopropyl triethoxysilanes) are slowly dropped to described mix Close in solution, wherein amino silicone and silicon P elements mol ratio in the solution containing nitrogen organic phosphonic acid are 4:7, hold at room temperature Continuous stirring 24h, obtains sol solutionses；
4) 1mL volumetric concentrations are slowly added into step 3 for 5% glutaraldehyde solution) obtained by sol solutionses in, stirring 1 ~2h obtains coagulant liquid；
5) by step 4) obtained coagulant liquid poured into polytetrafluoroethylene (PTFE) mould, and 2~3 days are aged at room temperature after 80 DEG C Baking oven in dry 1~2 day, then 2~4h is separately dried with 150 DEG C in 100 DEG C, 120 DEG C successively, by film from poly- four after cooling Taken off in PVF mould, you can obtain cross-linked chitosan/nitrogenous phosphonic acids based polysiloxane high temperature proton exchange film.
Using with the same method of testing of embodiment one to cross-linked chitosan/poly- silica of nitrogenous phosphonate group obtained by the present embodiment The material of alkane high temperature proton exchange film is tested, the cross-linked chitosan made by the present embodiment/nitrogenous phosphonic acids based polysiloxane Silicon P elements mol ratio is 4 in high temperature proton exchange film:7, test Proton conducting under the conditions of 120 DEG C, relative humidity is 20% Rate is 0.084S/cm, and ion exchange capacity is 0.80mg/mol, and tensile strength is 41.2Mpa, and linear swelling coefficient is 8.84%, water absorption rate is 37.6%, and stability in use is good at 205 DEG C.

Claims (10)

1. a kind of cross-linked chitosan/nitrogenous phosphonic acids based polysiloxane high temperature proton exchange film, the film can be grown under the conditions of 200 DEG C Phase uses, it is characterised in that it is to use following steps products therefrom：
1) under normal temperature, Chitosan powder is dissolved in aqueous acetic acid, is sufficiently stirred for being uniformly dissolved it, obtains chitosan molten Liquid；
2) nitrogen organic phosphonic acid will be contained to be dissolved in deionized water, it is 0.17~1.50mol/L's that lasting stirring, which obtains concentration, at room temperature Solution containing nitrogen organic phosphonic acid；
3) at room temperature by step 2) gained solution containing nitrogen organic phosphonic acid is slowly dropped to step 1) obtained by chitosan solution, fully Mixed solution is uniformly mixing to obtain, wherein solution containing nitrogen organic phosphonic acid is 1 with chitosan solution volume ratio：1~2：1, then by ammonia Radical siloxane is slowly dropped in the mixed solution, wherein amino silicone and silicon, phosphorus in the solution containing nitrogen organic phosphonic acid Elemental mole ratios are 4:1~4:7, stir, obtain sol solutionses；
4) the aldehyde crosslinking agent aqueous solution is slowly added into step 3) gained sol solutionses in, wherein the aldehyde crosslinking agent aqueous solution with it is molten The volume ratio of glue is 1：10~1：20, it is uniformly mixing to obtain coagulant liquid；
5) by step 4) gained coagulant liquid pour into polytetrafluoroethylene (PTFE) mould, room temperature be aged 2~3 days after 80 DEG C drying, then It is shelled from polytetrafluoroethylene (PTFE) mould after cooling with being heat-treated 2~4h respectively under the conditions of 150 DEG C in 100 DEG C, 120 DEG C successively From i.e. obtain cross-linked chitosan/nitrogenous phosphonic acids based polysiloxane high temperature proton exchange film.
2. cross-linked chitosan according to claim 1/nitrogenous phosphonic acids based polysiloxane high temperature proton exchange film, its feature exists In step 1) the chitosan molecule amount be 5~70,000, deacetylation>85%, the aqueous acetic acid volumetric concentration be 1~ 2%, the chitosan solution mass concentration is 1~2%.
3. cross-linked chitosan according to claim 1/nitrogenous phosphonic acids based polysiloxane high temperature proton exchange film, its feature exists In step 2) described containing nitrogen organic phosphonic acid it is ATMP, ethylene diamine tetra methylene phosphonic acid, hexapotassium One kind.
4. cross-linked chitosan according to claim 1/nitrogenous phosphonic acids based polysiloxane high temperature proton exchange film, its feature exists In step 3) amino silicone is one kind in 3- aminopropyl triethoxysilanes or 3- TSL 8330s.
5. cross-linked chitosan according to claim 1/nitrogenous phosphonic acids based polysiloxane high temperature proton exchange film, its feature exists In step 4) aldehyde crosslinking agent is one kind in glutaraldehyde or glyoxal, aldehyde crosslinking agent aqueous solution volumetric concentration is 1~ 5%.
6. a kind of preparation method of cross-linked chitosan/nitrogenous phosphonic acids based polysiloxane high temperature proton exchange film, the film is in 200 DEG C of bars It can be used for a long time under part, it is characterised in that step is as follows：
1) under normal temperature, Chitosan powder is dissolved in aqueous acetic acid, is sufficiently stirred for being uniformly dissolved it, obtains chitosan molten Liquid；
2) nitrogen organic phosphonic acid will be contained to be dissolved in deionized water, it is 0.17~1.50mol/L's that lasting stirring, which obtains concentration, at room temperature Solution containing nitrogen organic phosphonic acid；
3) at room temperature by step 2) gained solution containing nitrogen organic phosphonic acid is slowly dropped to step 1) obtained by chitosan solution, fully Mixed solution is uniformly mixing to obtain, wherein solution containing nitrogen organic phosphonic acid is 1 with chitosan solution volume ratio：1~2：1, then by ammonia Radical siloxane is slowly dropped in the mixed solution, wherein amino silicone and silicon, phosphorus in the solution containing nitrogen organic phosphonic acid Elemental mole ratios are 4:1~4:7, stir, obtain sol solutionses；
4) the aldehyde crosslinking agent aqueous solution is slowly added into step 3) gained sol solutionses in, wherein the aldehyde crosslinking agent aqueous solution with it is molten The volume ratio of glue is 1：10~1：20, it is uniformly mixing to obtain coagulant liquid；
5) by step 4) gained coagulant liquid pour into polytetrafluoroethylene (PTFE) mould, room temperature be aged 2~3 days after 80 DEG C drying, then It is shelled from polytetrafluoroethylene (PTFE) mould after cooling with being heat-treated 2~4h respectively under the conditions of 150 DEG C in 100 DEG C, 120 DEG C successively From i.e. obtain cross-linked chitosan/nitrogenous phosphonic acids based polysiloxane high temperature proton exchange film.
7. the preparation side of cross-linked chitosan according to claim 6/nitrogenous phosphonic acids based polysiloxane high temperature proton exchange film Method, it is characterised in that step 1) the chitosan molecule amount be 5~70,000, deacetylation>85%, the aqueous acetic acid volume Concentration is 1~2%, and the chitosan solution mass concentration is 1~2%.
8. the preparation side of cross-linked chitosan according to claim 6/nitrogenous phosphonic acids based polysiloxane high temperature proton exchange film Method, it is characterised in that step 2) it is described containing nitrogen organic phosphonic acid be ATMP, ethylene diamine tetra methylene phosphonic acid, hexamethylene diamine four One kind in methylenephosphonic acid.
9. the preparation side of cross-linked chitosan according to claim 6/nitrogenous phosphonic acids based polysiloxane high temperature proton exchange film Method, it is characterised in that step 3) amino silicone be 3- aminopropyl triethoxysilanes or 3- aminopropyl trimethoxy silicon One kind in alkane.
10. the preparation side of cross-linked chitosan according to claim 6/nitrogenous phosphonic acids based polysiloxane high temperature proton exchange film Method, it is characterised in that step 4) aldehyde crosslinking agent is one kind in glutaraldehyde or glyoxal, aldehyde crosslinking agent aqueous liquid Product concentration is 1~5%.
CN201410785191.7A 2014-12-16 2014-12-16 A kind of cross-linked chitosan/nitrogenous phosphonic acids based polysiloxane high temperature proton exchange film and preparation method thereof Expired - Fee Related CN104538657B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410785191.7A CN104538657B (en) 2014-12-16 2014-12-16 A kind of cross-linked chitosan/nitrogenous phosphonic acids based polysiloxane high temperature proton exchange film and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410785191.7A CN104538657B (en) 2014-12-16 2014-12-16 A kind of cross-linked chitosan/nitrogenous phosphonic acids based polysiloxane high temperature proton exchange film and preparation method thereof

Publications (2)

Publication Number Publication Date
CN104538657A CN104538657A (en) 2015-04-22
CN104538657B true CN104538657B (en) 2017-08-25

Family

ID=52854152

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410785191.7A Expired - Fee Related CN104538657B (en) 2014-12-16 2014-12-16 A kind of cross-linked chitosan/nitrogenous phosphonic acids based polysiloxane high temperature proton exchange film and preparation method thereof

Country Status (1)

Country Link
CN (1) CN104538657B (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10618014B2 (en) * 2015-05-29 2020-04-14 Asahi Kasei Kabushiki Kaisha Gas separation memebrane
CN107834089B (en) * 2017-10-19 2022-02-18 武汉氢阳能源有限公司 High-temperature proton exchange membrane for membrane fuel cell and preparation method and application thereof
CN108155406B (en) * 2017-12-26 2021-04-06 中国科学院青岛生物能源与过程研究所 Phosphosilicate glass doped chitosan intermediate-temperature proton exchange membrane and preparation method thereof
CN109818024B (en) * 2019-01-30 2020-12-08 湖北工程学院 Composite proton exchange membrane and preparation method thereof
CN115160538B (en) * 2022-07-09 2023-03-31 四川大学 Crosslinked PDMS/chitosan composite material and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1775838A (en) * 2005-12-15 2006-05-24 北京航空航天大学 Method for preparing chitose proton exchange membrance for fuel cell
CN101807703A (en) * 2010-03-18 2010-08-18 武汉理工大学 Intermediate-temperature proton exchange film of organic polysiloxane phosphonic acid group and preparation method thereof
CN103531831A (en) * 2013-08-16 2014-01-22 武汉理工大学 Acid-base type amino polyphosphonate polysiloxane medium-temperature proton exchange membrane material and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1775838A (en) * 2005-12-15 2006-05-24 北京航空航天大学 Method for preparing chitose proton exchange membrance for fuel cell
CN101807703A (en) * 2010-03-18 2010-08-18 武汉理工大学 Intermediate-temperature proton exchange film of organic polysiloxane phosphonic acid group and preparation method thereof
CN103531831A (en) * 2013-08-16 2014-01-22 武汉理工大学 Acid-base type amino polyphosphonate polysiloxane medium-temperature proton exchange membrane material and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
不同交联剂含量对戊二醛交联壳聚糖膜结构与性能影响的研究;陈新，邵正中等;《化学学报》;20001231;第58卷(第12期);全文 *

Also Published As

Publication number Publication date
CN104538657A (en) 2015-04-22

Similar Documents

Publication Publication Date Title
CN104538657B (en) A kind of cross-linked chitosan/nitrogenous phosphonic acids based polysiloxane high temperature proton exchange film and preparation method thereof
CN102891335B (en) Preparation method of full-solid-state nano composite polymer electrolyte
CN104485470B (en) A kind of polysiloxanes polyphosphonic acid doping shitosan high temperature proton exchange film and preparation method thereof
CN103531831B (en) Temperature proton exchange film material and preparation method thereof in a kind of soda acid type aminopolyphosphonic acid polysiloxanes
CN103435828B (en) Graphene oxide silicon dioxide compound/polymer hybridization proton exchange membrane of sulfonation and preparation method thereof
CN103408760B (en) A kind of middle temperature proton exchange film material and preparation method thereof and the fuel cell using this material to prepare
CN109535457B (en) Preparation method of sulfonated polyether ether ketone/sulfonated graphene oxide composite proton exchange membrane
CN103700874B (en) A kind of in-situ modified polybenzimidazoles PEM of inorganic nano-particle and preparation method thereof
CN107104242A (en) A kind of polysiloxanes polyphosphonic acid doping universal PEM of SPEEK high/low temperatures and preparation method thereof
CN103897221A (en) Chitosan/phosphorylated silicon dioxide particle hybrid film as well as preparation and application thereof
CN103012824A (en) Graphene oxide-polymer hybrid proton exchange membrane and preparation method thereof
CN110041552A (en) Compound high temperature proton exchange film and preparation method thereof based on sulfonation aryl oxide type polybenzimidazoles Yu sulfonation polysilsesquioxane
CN105037733B (en) A kind of phosphoric acid radical siloxane high temperature proton exchange film of hydrolysis-stable and preparation method thereof
Terbish et al. Improved performance of organic–inorganic nanocomposite membrane for bioelectricity generation and wastewater treatment in microbial fuel cells
CN103700873B (en) Inorganic nanoparticle in-situ modified polybenzimidazole derivative proton exchange membrane and preparation method thereof
CN108948436A (en) A kind of preparation method of the modified composite membrane of sodium alginate-pectin
Chen et al. Cross-linked zwitterionic polyelectrolytes based on sulfonated poly (ether sulfone) with high proton conductivity for direct methanol fuel cells
Divya et al. Sulfonated Chitosan and HKUST‐1 metal organic frameworks based hybrid membranes for direct methanol fuel cell applications
CN107834089A (en) A kind of high temperature proton exchange film available for membrane cell and its preparation method and application
CN108376791B (en) Organic-inorganic composite proton exchange membrane containing double proton conductors and preparation method thereof
CN104497238A (en) Phosphoric acid-grafted segmented copolymer high-temperature proton exchange membrane and preparation method thereof
CN105017545B (en) A kind of polysiloxane grafted phosphonic acid base Copolymer proton exchange membrane and preparation method thereof
CN105098215B (en) A kind of phosphonic acids radical siloxane PEM of hydrolysis-stable and preparation method thereof
CN114031870B (en) Proton exchange membrane and preparation method and application thereof
JP4645196B2 (en) Organic-inorganic composite ion conducting membrane

Legal Events

Date Code Title Description
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20170825

Termination date: 20171216