CN105694088A - Application and preparation method of polyvinyl alcohol/chitosan solid electrolyte film - Google Patents

Application and preparation method of polyvinyl alcohol/chitosan solid electrolyte film Download PDF

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CN105694088A
CN105694088A CN201610219938.1A CN201610219938A CN105694088A CN 105694088 A CN105694088 A CN 105694088A CN 201610219938 A CN201610219938 A CN 201610219938A CN 105694088 A CN105694088 A CN 105694088A
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chitosan
polyvinyl alcohol
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CN105694088B (en
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江献财
孙玉俊
胡海凤
侯琳熙
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Fuzhou University
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    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1041—Polymer electrolyte composites, mixtures or blends
    • 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
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    • H01M8/1044—Mixtures of polymers, of which at least one is ionically conductive
    • H—ELECTRICITY
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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
    • 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
    • H01M8/1069—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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    • C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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Abstract

The invention discloses application and a preparation method of a polyvinyl alcohol/chitosan solid electrolyte film. By adoption of Lewis acidic inorganic salt aluminum chloride aqueous solution capable of simultaneously dissolving chitosan and a plasticized modified polyvinyl alcohol/chitosan composite material as a chitosan solvent, utilization of volatile organic acids such as acetic acid in dissolution of chitosan is avoided, and an original polyvinyl alcohol/chitosan composite film is prepared; the original polyvinyl alcohol/chitosan composite film is subsequently soaked into a formaldehyde solution to realize crosslinking, and the crosslinked polyvinyl alcohol/chitosan composite film is soaked into a NaOH solution to realize modification so as to obtain the polyvinyl alcohol/chitosan solid electrolyte film. The polyvinyl alcohol/chitosan solid electrolyte film prepared according to the method has excellent water resistance and dimensional stability; ionic conductivity of the film is greatly improved up to 1.06*10<-2>(S.cm<-1>), and the methanol permeability reaches 5.23*10<-6>(cm<2>.s<-1>).

Description

The preparation method of a kind of polyvinyl alcohol/chitosan solid electrolytic thin-membrane and application
Technical field
The invention belongs to material preparation and technical field of electrochemistry, particularly to preparation method and the application of a kind of polyvinyl alcohol/chitosan solid electrolytic thin-membrane。
Background technology
Polymer electrolyte film can not only be used for solid electrolyte, can stop again the infiltration of material between galvanic anode and negative electrode, has increasingly becomed the Primary Component obtaining high performance fuel cell。Nafion barrier film is considered as the state-of-the-art polymer electrolyte film for DMFC。The chemically and physically stability that Nafion thin film has had, and there is high proton conductivity。But Nafion thin film is expensive, and business-like Nafion thin film has significantly high methanol permeability problem, and when using Nafion thin film to make barrier film, methanol easily penetrates into negative pole from positive pole。
Polyvinyl alcohol is a kind of semicrystalline polymeric, has good chemical stability, hydrophilic, corrosion resistance and preferably mechanical property and polyvinyl alcohol wide material sources, and price is relatively low。Polyvinyl alcohol as a kind of water-soluble high-molecular material, because it has good water solublity, film property, cementability, emulsibility and barrier, and is widely used in the fields such as fiber, thin film, gel。
Chitosan is to there is the Main Derivatives next in number only to cellulosic second largest natural macromolecular material chitin on the earth。Chitosan is by the product of chitosan moiety N-deacetylation, is also the topmost derivant of chitin。Chitosan is a kind of water miscible natural polymer, there is the film property of excellence, antibiotic property and good biodegradable and biocompatibility, and some electroactive substance is had very strong chelating, absorption and ion exchange by the reactive group of chitosan (amino and hydroxyl) so that chitosan all demonstrates very strong application prospect in fields such as thin film, fiber, hydrogels。
Polyvinyl alcohol/chitosan laminated film can be prepared by after polyvinyl alcohol and chitosan compound, and this laminated film has good mechanical property and thermal stability。Polyvinyl alcohol and chitosan have good methanol barrier property, and the polyvinyl alcohol prepared/chitosan laminated film also has good methanol barrier property。Containing substantial amounts of amino and hydroxyl on polyvinyl alcohol and chitosan molecule chain so that polyvinyl alcohol/chitosan laminated film has good ionic conducting property。Polyvinyl alcohol/chitosan film is expected to be applied in solid electrolyte film field, prepares solid electrolyte film with polyvinyl alcohol and chitosan for raw material and has very big cost advantage。
Summary of the invention
Present invention aims to the deficiencies in the prior art, it is provided that the preparation method of a kind of polyvinyl alcohol/chitosan solid electrolytic thin-membrane。Prepared polyvinyl alcohol/chitosan solid electrolytic thin-membrane has good water resistance and dimensional stability, and the ionic conductivity of thin film is greatly enhanced, and ionic conductivity reaches 1.06 × 10-2(S·cm-1), methanol permeability reaches 5.23 × 10-6(cm2·s-1)。
For achieving the above object, the present invention adopts the following technical scheme that
The preparation method of a kind of polyvinyl alcohol/chitosan solid electrolytic thin-membrane, it specifically comprises the following steps that
(1) being dissolved in aluminum chloride aqueous solution by chitosan, stirring in water bath prepares chitosan solution, is added by polyvinyl alcohol in deionized water, and stirring in water bath prepares poly-vinyl alcohol solution, by gained chitosan solution and blended under agitation 0.5h under poly-vinyl alcohol solution water-bath；
(2) step (1) gained mixed solution vacuum drying 48h at 50 ~ 60 DEG C is obtained polyvinyl alcohol/chitosan film；
(3) polyvinyl alcohol/chitosan film of step (2) gained is joined in the mixed solution of formaldehyde and acetone, described formaldehyde and the mixed solution of acetone are also added into salt acid as catalyst, wherein formaldehyde: acetone: the volume ratio of hydrochloric acid is 1:2:0.01, take out after cross-linking reaction 1h, and remove the organic solvent remaining in film surface 3 times with deionized water rinsing, obtain the polyvinyl alcohol/chitosan film of formaldehyde crosslinking；
(4) polyvinyl alcohol/chitosan film of the formaldehyde crosslinking of preparation in step (3) after dry 24h, is put into and soaked 2h in NaOH solution at 25 DEG C, prepare polyvinyl alcohol/chitosan solid electrolytic thin-membrane in 50 DEG C of vacuum drying ovens。
In liquor alumini chloridi described in step (1), the mass fraction of aluminum chloride is 1wt% ~ 3wt%, and in chitosan solution, the mass fraction of chitosan is 2wt% ~ 5wt%, and poly-vinyl alcohol solution mass fraction is 5wt% ~ 10wt%。
The mass ratio of polyvinyl alcohol affiliated in step (1) and chitosan is 2 ~ 4:1。
In step (3), polyvinyl alcohol/chitosan film is 1:10 ~ 20 with the mass ratio of formaldehyde and the mixed solution of acetone。
In step (1), bath temperature is 85 ~ 90 DEG C。
The NaOH solution mass fraction used in step (4) is 30wt% ~ 40wt%。
Prepared polyvinyl alcohol/chitosan solid electrolytic thin-membrane is for direct solid fuel cell barrier film field。
The beneficial effects of the present invention is:
(1) polyvinyl alcohol of the present invention/chitosan solid electrolytic thin-membrane adopts aluminum chloride aqueous solution to be chitosan solvent, prepares thin film by solution film formation, and adopts the mode that post processing cross-links to improve water resistance and the dimensional stability of polyvinyl alcohol/chitosan；
(2) chitosan solvent aluminum chloride aqueous solution also can provide chloride ion for polyvinyl alcohol/chitosan film, reduces the crystal property of polyvinyl alcohol/chitosan film, improves the ionic conductivity of polyvinyl alcohol/chitosan film, and ionic conductivity reaches 1.06 × 10-2(S·cm-1), methanol permeability reaches 5.23 × 10-6(cm2·s-1)；
(3) polyvinyl alcohol provided by the invention/chitosan solid electrolytic thin-membrane can be used for the fields such as methanol fuel cell barrier film, may replace Nafion thin film, is substantially reduced its cost。
Detailed description of the invention
Below by specific embodiment, the present invention is specifically described。Be necessary it is pointed out here that be that following example are served only for the present invention is further described; it is not intended that limiting the scope of the invention, the present invention can be made some nonessential improvement and adjustment according to foregoing invention content by the person skilled in the art in this field。
Embodiment 1
(1) being dissolved in 1wt% aluminum chloride aqueous solution by 2.0g chitosan, stir 2h and dissolve, prepare chitosan solution at water-bath 90 DEG C, the mass fraction of chitosan is 2wt%；Being added by 4.0g polyvinyl alcohol in deionized water, stir 2h, obtain poly-vinyl alcohol solution at water-bath 90 DEG C, poly-vinyl alcohol solution mass fraction is 5wt%；By gained chitosan solution and blended 0.5h under 85 DEG C of water-baths of poly-vinyl alcohol solution；
(2) step (1) gained mixed solution vacuum drying 48h at 60 DEG C is obtained polyvinyl alcohol/chitosan film；
(3) polyvinyl alcohol/chitosan film of step (2) gained is joined in the mixed solution of formaldehyde and acetone, described formaldehyde and the mixed solution of acetone are also added into salt acid as catalyst, wherein formaldehyde: acetone: the volume ratio of hydrochloric acid is 1:2:0.01, take out after cross-linking reaction 1h, and remove the organic solvent remaining in film surface 3 times with deionized water rinsing, obtain the polyvinyl alcohol/chitosan film of formaldehyde crosslinking；
(4) by the polyvinyl alcohol/chitosan film of the formaldehyde crosslinking of preparation in step (3) in 50 DEG C of vacuum drying ovens dried, put into and 40wt%NaOH solution soak at 25 DEG C 2h, prepare polyvinyl alcohol/chitosan polymer electrolytic thin-membrane。
In step (3), polyvinyl alcohol/chitosan film is 1:10 with the mass ratio of formaldehyde and the mixed solution of acetone。
Embodiment 2
(1) being dissolved in 3wt% aluminum chloride aqueous solution by 2.0g chitosan, stir 2h and dissolve, prepare chitosan solution at water-bath 88 DEG C, the mass fraction of chitosan is 3wt%；Being added by 8.0g polyvinyl alcohol in deionized water, stir 2h, obtain poly-vinyl alcohol solution at water-bath 90 DEG C, poly-vinyl alcohol solution mass fraction is 8wt%；By gained chitosan solution and blended 0.5h under 88 DEG C of water-baths of poly-vinyl alcohol solution；
(2) step (1) gained mixed solution vacuum drying 48h at 50 DEG C is obtained polyvinyl alcohol/chitosan film；
(3) polyvinyl alcohol/chitosan film of step (2) gained is joined in the mixed solution of formaldehyde and acetone, described formaldehyde and the mixed solution of acetone are also added into salt acid as catalyst, wherein formaldehyde: acetone: the volume ratio of hydrochloric acid is 1:2:0.01, take out after cross-linking reaction 1h, and remove the organic solvent remaining in film surface 3 times with deionized water rinsing, obtain the polyvinyl alcohol/chitosan film of formaldehyde crosslinking；
(4) by the polyvinyl alcohol/chitosan film of the formaldehyde crosslinking of preparation in step (3) in 50 DEG C of vacuum drying ovens dried, put into and 30wt%NaOH solution soak at 25 DEG C 2h, prepare polyvinyl alcohol/chitosan polymer electrolytic thin-membrane。
In step (3), polyvinyl alcohol/chitosan film is 1:15 with the mass ratio of formaldehyde and the mixed solution of acetone。
Embodiment 3
(1) being dissolved in 1wt% aluminum chloride aqueous solution by 2.0g chitosan, stir 2h and dissolve, prepare chitosan solution at water-bath 85 DEG C, the mass fraction of chitosan is 5wt%；Being added by 6.0g polyvinyl alcohol in deionized water, stir 2h, obtain poly-vinyl alcohol solution at water-bath 90 DEG C, poly-vinyl alcohol solution mass fraction is 10wt%；By gained chitosan solution and blended 0.5h under 90 DEG C of water-baths of poly-vinyl alcohol solution；
(2) step (1) gained mixed solution vacuum drying 48h at 55 DEG C is obtained polyvinyl alcohol/chitosan film；
(3) polyvinyl alcohol/chitosan film of step (2) gained is joined in the mixed solution of formaldehyde and acetone, described formaldehyde and the mixed solution of acetone are also added into salt acid as catalyst, wherein formaldehyde: acetone: the volume ratio of hydrochloric acid is 1:2:0.01, take out after cross-linking reaction 0.5h, and remove the organic solvent remaining in film surface 3 times with deionized water rinsing, obtain the polyvinyl alcohol/chitosan film of formaldehyde crosslinking；
(4) by the polyvinyl alcohol/chitosan film of the formaldehyde crosslinking of preparation in step (3) in 50 DEG C of vacuum drying ovens dried, put into and 35wt%NaOH solution soak at 25 DEG C 2h, prepare polyvinyl alcohol/chitosan polymer electrolytic thin-membrane。
In step (3), polyvinyl alcohol/chitosan film is 1:20 with the mass ratio of formaldehyde and the mixed solution of acetone。
Performance test
Polyvinyl alcohol/chitosan is for the research of methanol fuel cell barrier film。
Being used for detecting its ionic conductivity and methanol permeability by the polyvinyl alcohol prepared by embodiment 2/chitosan laminated film, its experimental procedure is as follows:
The ionic conductivity of thin film is recorded by double; two probe AC impedance spectrometries on electrochemical apparatus, and test frequency range is 0.1 ~ 1Hz。Before test, polyvinyl alcohol/chitosan film is put into immersion 48h in deionized water。Electrochemical workstation is placed in the chest being placed with deionized water during test, to ensure that test records under 100% humidity。Ionic conductivity б (the S cm of laminated film-1) it is calculated as follows:
б=l/Rb*A
In formula,lIt it is the distance (cm) between two stainless steel electrodes；A is the cross-sectional area (cm of thin film2)；RbFor ohmic internal resistance (Ω), AC impedence method record。
The methanol permeability of laminated film adopts disperser to record。Disperser contains supply tank and receiving slit, is placed with 2M methanol aqueous solution in supply tank, is placed with deionized water in receiving slit。Equipped with the polyvinyl alcohol/chitosan laminated film soaking 24h in deionized water in the middle of two grooves。Supply tank and receiving slit are equipped with magnetic agitation。Based on concentration difference, methanol can spread from supply tank to receiving slit。Every the set time into the liquid in receiving slit all changed deionized water, and measure methanol concentration in receiving slit solution by gas chromatographic analysis。The methanol permeability of laminated film is calculated by following formula:
In formula, P is expanding coefficient (cm2·s-1), CBT () is the methanol concentration in receiving slit under t, toFor initial time, CAFor the initial methanol concentration in supply tank, V is the volume of supply tank or receiving slit。A is effective infiltrating area, and L is effective permeability-thickness。
Subordinate list 1 gives methanol permeability and the ionic conductivity of polyvinyl alcohol/chitosan laminated film
The foregoing is only presently preferred embodiments of the present invention, all equalizations done according to the present patent application the scope of the claims change and modify, and all should belong to the covering scope of the present invention。

Claims (7)

1. the preparation method of polyvinyl alcohol/chitosan solid electrolytic thin-membrane, it is characterised in that specifically comprise the following steps that
(1) being dissolved in aluminum chloride aqueous solution by chitosan, stirring in water bath prepares chitosan solution, is added by polyvinyl alcohol in deionized water, and stirring in water bath prepares poly-vinyl alcohol solution, by gained chitosan solution and blended under agitation 0.5h under poly-vinyl alcohol solution water-bath；
(2) step (1) gained mixed solution vacuum drying 48h at 50 ~ 60 DEG C is obtained polyvinyl alcohol/chitosan film；
(3) polyvinyl alcohol/chitosan film of step (2) gained is joined in the mixed solution of formaldehyde and acetone, described formaldehyde and the mixed solution of acetone are also added into salt acid as catalyst, wherein formaldehyde: acetone: the volume ratio of hydrochloric acid is 1:2:0.01, take out after cross-linking reaction 1h, and remove the organic solvent remaining in film surface 3 times with deionized water rinsing, obtain the polyvinyl alcohol/chitosan film of formaldehyde crosslinking；
(4) polyvinyl alcohol/chitosan film of the formaldehyde crosslinking of preparation in step (3) after dry 24h, is put into and soaked 2h in NaOH solution at 25 DEG C, prepare polyvinyl alcohol/chitosan solid electrolytic thin-membrane in 50 DEG C of vacuum drying ovens。
2. the preparation method of a kind of polyvinyl alcohol/chitosan solid electrolytic thin-membrane according to claim 1, it is characterized in that: in liquor alumini chloridi described in step (1), the mass fraction of aluminum chloride is 1wt% ~ 3wt%, in chitosan solution, the mass fraction of chitosan is 2wt% ~ 5wt%, and poly-vinyl alcohol solution mass fraction is 5wt% ~ 10wt%。
3. the preparation method of a kind of polyvinyl alcohol/chitosan solid electrolytic thin-membrane according to claim 1, it is characterised in that: the mass ratio of polyvinyl alcohol affiliated in step (1) and chitosan is 2 ~ 4:1。
4. the preparation method of a kind of polyvinyl alcohol/chitosan solid electrolytic thin-membrane according to claim 1, it is characterised in that: in step (3), polyvinyl alcohol/chitosan film is 1:10 ~ 20 with the mass ratio of formaldehyde and the mixed solution of acetone。
5. the preparation method of a kind of polyvinyl alcohol/chitosan solid electrolytic thin-membrane according to claim 1, it is characterised in that: in step (1), bath temperature is 85 ~ 90 DEG C。
6. the preparation method of a kind of polyvinyl alcohol/chitosan solid electrolytic thin-membrane according to claim 1, it is characterised in that: the NaOH solution mass fraction used in step (4) is 30wt% ~ 40wt%。
7. the application of polyvinyl alcohol/chitosan solid electrolytic thin-membrane that a preparation method as claimed in claim 1 prepares, it is characterised in that: prepared polyvinyl alcohol/chitosan solid electrolytic thin-membrane is used for direct solid fuel cell barrier film field。
CN201610219938.1A 2016-04-11 2016-04-11 A kind of preparation method and application of polyvinyl alcohol/chitosan solid electrolytic thin-membrane Expired - Fee Related CN105694088B (en)

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CN107715855A (en) * 2017-11-15 2018-02-23 福州大学 A kind of porous carbon materials for being used for organic dyestuff and fluoride wastewater treatment and preparation method thereof
CN107895812A (en) * 2017-11-16 2018-04-10 浙江中科立德新材料有限公司 A kind of solid electrolyte film preparation method based on the macromolecule modified gelatin polymer of natural polysaccharide
CN108774327A (en) * 2018-05-25 2018-11-09 湖州斯蔓生物材料有限公司 It is used to prepare the method for PVA hydrogels, using the PVA hydrogels and composite material of its preparation
CN108823983A (en) * 2018-05-29 2018-11-16 福州大学 A kind of preparation method of quaternized polyvinyl alcohol/chitosan electrostatic spinning solid electrolyte film
CN109088032A (en) * 2018-06-28 2018-12-25 中国地质大学（武汉） A kind of polyvinyl alcohol lithium battery diaphragm and preparation method thereof based on chitosan
CN109135141A (en) * 2018-08-29 2019-01-04 佛山市森昂生物科技有限公司 A kind of preparation method of Halogen-free flame-retardant polyvinyl alcohol film
CN109181179A (en) * 2018-07-03 2019-01-11 海南大学 A kind of crust liquefied substance/degradation plastic blend film and preparation method thereof
CN114477783A (en) * 2022-01-14 2022-05-13 中山爱因新材料有限公司 Composite material and preparation method and application thereof
CN114477783B (en) * 2022-01-14 2024-06-07 中山爱因新材料有限公司 Composite material and preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101418080A (en) * 2008-11-13 2009-04-29 北京科技大学 Method for preparing chitosan proton exchange membrane for hydrogen sensor
CN103601904A (en) * 2013-11-21 2014-02-26 福州大学 Preparation method of chitosan/polyvinyl alcohol composite material

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101418080A (en) * 2008-11-13 2009-04-29 北京科技大学 Method for preparing chitosan proton exchange membrane for hydrogen sensor
CN103601904A (en) * 2013-11-21 2014-02-26 福州大学 Preparation method of chitosan/polyvinyl alcohol composite material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
M.H. BURAIDAH: ""Characterization of chitosan/PVA blended electrolyte doped with NH4I"", 《JOURNAL OF NON-CRYSTALLINE SOLIDS》 *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107715855A (en) * 2017-11-15 2018-02-23 福州大学 A kind of porous carbon materials for being used for organic dyestuff and fluoride wastewater treatment and preparation method thereof
CN107895812A (en) * 2017-11-16 2018-04-10 浙江中科立德新材料有限公司 A kind of solid electrolyte film preparation method based on the macromolecule modified gelatin polymer of natural polysaccharide
CN108774327A (en) * 2018-05-25 2018-11-09 湖州斯蔓生物材料有限公司 It is used to prepare the method for PVA hydrogels, using the PVA hydrogels and composite material of its preparation
CN108823983A (en) * 2018-05-29 2018-11-16 福州大学 A kind of preparation method of quaternized polyvinyl alcohol/chitosan electrostatic spinning solid electrolyte film
CN108823983B (en) * 2018-05-29 2020-07-07 福州大学 Preparation method of quaternized polyvinyl alcohol/chitosan electrostatic spinning solid electrolyte film
CN109088032A (en) * 2018-06-28 2018-12-25 中国地质大学（武汉） A kind of polyvinyl alcohol lithium battery diaphragm and preparation method thereof based on chitosan
CN109181179A (en) * 2018-07-03 2019-01-11 海南大学 A kind of crust liquefied substance/degradation plastic blend film and preparation method thereof
CN109135141A (en) * 2018-08-29 2019-01-04 佛山市森昂生物科技有限公司 A kind of preparation method of Halogen-free flame-retardant polyvinyl alcohol film
CN114477783A (en) * 2022-01-14 2022-05-13 中山爱因新材料有限公司 Composite material and preparation method and application thereof
CN114477783B (en) * 2022-01-14 2024-06-07 中山爱因新材料有限公司 Composite material and preparation method and application thereof

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