CN108598539B - A kind of electrolyte diaphragm for vanadium cell and preparation method thereof - Google Patents
A kind of electrolyte diaphragm for vanadium cell and preparation method thereof Download PDFInfo
- Publication number
- CN108598539B CN108598539B CN201810287140.XA CN201810287140A CN108598539B CN 108598539 B CN108598539 B CN 108598539B CN 201810287140 A CN201810287140 A CN 201810287140A CN 108598539 B CN108598539 B CN 108598539B
- Authority
- CN
- China
- Prior art keywords
- preparation
- vanadium cell
- electrolyte
- diaphragm
- vanadium
- 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.)
- Active
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
- H01M8/10—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
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1046—Mixtures of at least one polymer and at least one additive
- H01M8/1048—Ion-conducting additives, e.g. ion-conducting particles, heteropolyacids, metal phosphate or polybenzimidazole with phosphoric acid
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
-
- 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
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Composite Materials (AREA)
- Conductive Materials (AREA)
- Fuel Cell (AREA)
Abstract
The present invention provides a kind of preparation method of electrolyte diaphragm for vanadium cell, includes the following steps: the preparation of one) quaternary silane, two) preparation of polymer, the three) preparation of diaphragm.The invention also discloses the electrolyte diaphragm for vanadium cell being prepared according to the preparation method of the electrolyte diaphragm for vanadium cell and using the electrolyte diaphragm for vanadium cell as the vanadium cell of electrolyte membrance.The electrolyte diaphragm for vanadium cell that the present invention is prepared is compared with conventional quaternary ammonium salts anion-exchange membrane in the prior art, price is cheaper, mechanical mechanics property, chemical stability and thermal stability are more preferable, hinder vanadium performance more preferably, ionic conductivity is higher, deformation is small, meets vanadium cell electrolyte membrance requirement.
Description
Technical field
The invention belongs to polyelectrolyte material technical fields, are related to a kind of vanadium cell component, specifically, being related to a kind of vanadium
Electrolyte for batteries diaphragm and preparation method thereof.
Background technique
In recent years, with the development of economy and the propulsion of global industry process, energy problem and environmental problem are increasingly tight
It is high, become an important factor for restricting social progress.Carrying out energy-saving, reinforcement water energy, wind energy, solar energy, tide energy etc. can be again
The development and utilization of the raw energy and nuclear energy is the important channel for solving this two big world property problem.Wind energy, solar energy etc. these can
The utilization of the renewable sources of energy be unable to do without efficient, the cheap, energy storage technology of pollution less and securely and reliably.All-vanadium flow battery is due to it
With can deep charge point, energy efficiency be high, environmentally protective, fast response time, Capacity design are independent, without territory restriction, service life
The advantages that long, at low cost, it is considered to be one of most promising extensive energy storage technology at this stage.
Critical material one of of the electrolyte diaphragm for vanadium cell as vanadium cell, the electrolyte that can not only be positive liquid provide from
The transmission channel of son, but also self-discharge of battery effect caused by the cross contamination of positive and negative anodes electrolyte can be prevented.Its property
The quality of energy directly affects the battery efficiency and service life cycle of vanadium cell.Electrolyte diaphragm for vanadium cell has become vanadium electricity
The bottleneck of pond development, currently, this film of Nafion membrane for the mainly E.I.Du Pont Company production that vanadium cell uses is mainly by import, valence
Lattice are expensive, and the phenomenon of osmosis of its vanadium ion in the electrolytic solution is easy to cause the self discharge effect of battery to reduce electricity than more serious
Pond efficiency causes energy loss, and swelling set is big, influences the assembling sealing of vanadium cell.
Anion-exchange membrane is one of electrolyte diaphragm for vanadium cell, in the charged group and solution being had due to it
Vanadium ion it is mutually exclusive, resistance vanadium effect is prominent, causes extensive concern in the industry.The preparation of conventional anion exchange membrane at present
Method needs to carry out chloromethylation to polymer film with chloromethylether, then obtains quaternary ammonium group with trimethylamine is quaternized.But chlorine
Methyl ether is a kind of extremely toxic substance, so that the preparation of anion-exchange membrane has very big harm to human body and environment.And tradition yin
Amberplex mechanical mechanics property, thermal stability and chemical stability need to be further increased.
Therefore, it is cheap to develop one kind, mechanical mechanics property, thermal stability, resistance vanadium and chemical stability are excellent
Electrolyte diaphragm for vanadium cell accords with the demands of the market, and has extensive market value and application prospect.
Summary of the invention
The main purpose of the present invention is to provide electrolyte diaphragm for vanadium cell and preparation method thereof, the preparation method is simple
Easy, of less demanding to equipment and reaction condition, raw material is easy to get, cheap, the electrolyte membrance being prepared and existing skill
Conventional quaternary ammonium salts anion-exchange membrane in art is compared, and price is cheaper, mechanical mechanics property, chemical stability and thermostabilization
Property it is more preferable, resistance vanadium performance more preferably, ionic conductivity is higher, and deformation is small, meets vanadium cell electrolyte membrance requirement.
To achieve the above objectives, the present invention provides a kind of preparation method of electrolyte diaphragm for vanadium cell, including walks as follows
It is rapid:
1) preparation of quaternary silane: epoxychloropropane is added in three-necked flask, slowly with constant pressure funnel
Bis- (diethylamino) silane are added dropwise, in 50-60 DEG C of back flow reaction about 6-8h, revolving removes excessive epoxychloropropane, third
Recrystallized 3-5 times in ketone, after again revolving remove acetone, obtain quaternary silane；
2) quaternary silane, the 4,4- dihydroxydiphenylsulisomer being prepared in step 1) preparation of polymer: will be passed through
It is dissolved in high boiling solvent, waits after being completely dissolved, catalyst is added, in nitrogen or atmosphere of inert gases, temperature is 90-100 DEG C
Under be stirred to react 6-8 hours, after settle out in acetone, and ethanol washing product 3-5 times is placed at 60-80 DEG C of vacuum oven
It dries 10-15 hours；
3) preparation of diaphragm: polymer, the 1- allyl -3- vinyl imidazole salt, matter that will be prepared by step 2)
The aqueous isopropanol of chloroplatinic acid that amount score is 2-3% is dissolved in dimethyl sulfoxide, 10-15 minutes ultrasonic, after stirred at 70-80 DEG C
Mix reaction 1-2 hours, after be cast on mold, dried 10-15 hours in 80-90 DEG C of air dry oven, obtain diaphragm.
Preferably, epoxychloropropane described in step 1), bis- (diethylamino) silane mass ratio be (1.2-1.5):
1。
Preferably, quaternary silane described in step 2), 4,4- dihydroxydiphenylsulisomer, high boiling solvent, catalyst
Mass ratio is 1.44:1:(6-12): (0.5-1).
Preferably, the high boiling solvent is in dimethyl sulfoxide, n,N-Dimethylformamide, N-Methyl pyrrolidone
It is one or more of.
Preferably, the catalyst is selected from one of benzyl dimethylamine, tetrabutylammonium bromide, benzyltriethylammoinium chloride
Or it is several.
Preferably, the inert gas is selected from one or more of helium, neon, argon gas.
Preferably, polymer described in step 3), 1- allyl -3- vinyl imidazole salt, chloroplatinic acid aqueous isopropanol,
The mass ratio of dimethyl sulfoxide is (5-10): 1:(0.1-0.15): (50-100).
Preferably, the 1- allyl -3- vinyl imidazole salt is selected from 1- allyl -3- vinyl imidazole villaumite, 1- alkene
One or more of propyl -3- vinyl imidazole bromide.
A kind of electrolyte diaphragm for vanadium cell is prepared using the preparation method of the vanadium cell electrolyte membrance.
A kind of vanadium cell, using the electrolyte diaphragm for vanadium cell as electrolyte membrance.
Due to the application of the above technical scheme, the invention has the following advantages:
(1) preparation method of electrolyte diaphragm for vanadium cell disclosed by the invention, preparation method is simple, to equipment and
Reaction condition is of less demanding, low in raw material price, is suitble to large-scale production.
(2) electrolyte diaphragm for vanadium cell disclosed by the invention, with conventional quaternary ammonium salts anion exchange in the prior art
Film is compared, and price is cheaper, and mechanical mechanics property, chemical stability and thermal stability are more preferable, and more preferably, ion passes resistance vanadium performance
Conductance is higher, and deformation is small, meets vanadium cell electrolyte membrance requirement.
(3) middle on electrolyte diaphragm for vanadium cell disclosed by the invention, molecular backbone and side chain to introduce ion-exchange sites
Point is conducive to the ion-exchange capacity for improving film.
(4) electrolyte diaphragm for vanadium cell disclosed by the invention contains aromatic series sulfone and silane structure on main chain, so that poly-
Closing object has excellent comprehensive performance, and 1- allyl -3- vinyl imidazole salt plays crosslinked action as crosslinking agent when film forming,
Three-dimensional net structure is formed, the comprehensive performance of polymer film is further increased.
Specific embodiment
It is described below for disclosing the present invention so that those skilled in the art can be realized the present invention.It is excellent in being described below
Embodiment is selected to be only used as illustrating, it may occur to persons skilled in the art that other obvious modifications.
Embodiment 1
A kind of preparation method of electrolyte diaphragm for vanadium cell, includes the following steps:
1) preparation of quaternary silane: epoxychloropropane 12g is added in three-necked flask, slow with constant pressure funnel
Slow that bis- (diethylamino) silane 10g are added dropwise, in 50 DEG C of back flow reaction about 6h, revolving removes excessive epoxychloropropane, third
Recrystallized 3 times in ketone, after again revolving remove acetone, obtain quaternary silane；
2) quaternary silane 14.4g, 4,4- dihydroxy two being prepared in step 1) preparation of polymer: will be passed through
Benzene sulfone 10g is dissolved in dimethyl sulfoxide 60g, is waited after being completely dissolved, and benzyl dimethylamine 5g is added, and in nitrogen atmosphere, temperature is 90 DEG C
Under be stirred to react 6 hours, after settle out in acetone, and be placed on for ethanol washing product 3 times at 60 DEG C of vacuum oven dry it is 10 small
When；
3) preparation of diaphragm: polymer 5g, 1- allyl -3- vinyl imidazole villaumite that will be prepared by step 2)
1g, mass fraction be 2 the aqueous isopropanol 0.1g of chloroplatinic acid of % be dissolved in dimethyl sulfoxide 50g, ultrasound 10 minutes, after 70
Be stirred to react at DEG C 1 hour, after be cast on mold, dried 10 hours in 80 DEG C of air dry oven, obtain diaphragm.
A kind of electrolyte diaphragm for vanadium cell is prepared using the preparation method of the vanadium cell electrolyte membrance.
A kind of vanadium cell, using the electrolyte diaphragm for vanadium cell as electrolyte membrance.
Embodiment 2
A kind of preparation method of electrolyte diaphragm for vanadium cell, includes the following steps:
1) preparation of quaternary silane: epoxychloropropane 13g is added in three-necked flask, slow with constant pressure funnel
Slow that bis- (diethylamino) silane 10g are added dropwise, in 52 DEG C of back flow reaction about 6.5h, revolving removes excessive epoxychloropropane,
Recrystallized 4 times in acetone, after again revolving remove acetone, obtain quaternary silane；
2) quaternary silane 14.4g, 4,4- dihydroxy two being prepared in step 1) preparation of polymer: will be passed through
Benzene sulfone 10g is dissolved in n,N-Dimethylformamide 75g, is waited after being completely dissolved, and tetrabutylammonium bromide 6.5g is added, in helium-atmosphere
Enclose, temperature is to be stirred to react 6.5 hours at 93 DEG C, after settle out in acetone, and ethanol washing product 4 times are placed on vacuum drying
It is dried 12 hours at 65 DEG C of case；
3) preparation of diaphragm: polymer 7g, 1- allyl -3- vinyl imidazole bromide that will be prepared by step 2)
1g, the aqueous isopropanol 0.11g of chloroplatinic acid that mass fraction is 2.3% are dissolved in dimethyl sulfoxide 75g, ultrasound 12 minutes, after
Be stirred to react at 73 DEG C 1.2 hours, after be cast on mold, dried 12 hours in 83 DEG C of air dry oven, obtain diaphragm.
A kind of electrolyte diaphragm for vanadium cell is prepared using the preparation method of the vanadium cell electrolyte membrance.
A kind of vanadium cell, using the electrolyte diaphragm for vanadium cell as electrolyte membrance.
Embodiment 3
A kind of preparation method of electrolyte diaphragm for vanadium cell, includes the following steps:
1) preparation of quaternary silane: epoxychloropropane 13.5g is added in three-necked flask, constant pressure funnel is used
Bis- (diethylamino) silane 10g are slowly added dropwise, in 56 DEG C of back flow reaction about 7h, revolving removes excessive epoxychloropropane,
Recrystallized 5 times in acetone, after again revolving remove acetone, obtain quaternary silane；
2) quaternary silane 14.4g, 4,4- dihydroxy two being prepared in step 1) preparation of polymer: will be passed through
Benzene sulfone 10g is dissolved in N-Methyl pyrrolidone 95g, is waited after being completely dissolved, and benzyltriethylammoinium chloride 7.5g is added, in neon atmosphere
Enclose, temperature is to be stirred to react 7 hours at 96 DEG C, after settle out in acetone, and ethanol washing product 5 times are placed on vacuum oven
It is dried 13 hours at 71 DEG C；
3) preparation of diaphragm: polymer 8g, 1- allyl -3- vinyl imidazole villaumite that will be prepared by step 2)
1g, the aqueous isopropanol 0.13g of chloroplatinic acid that mass fraction is 2.7% are dissolved in dimethyl sulfoxide 85g, ultrasound 13 minutes, after
Be stirred to react at 77 DEG C 1.7 hours, after be cast on mold, dried 13.5 hours in 87 DEG C of air dry oven, obtain diaphragm.
A kind of electrolyte diaphragm for vanadium cell is prepared using the preparation method of the vanadium cell electrolyte membrance.
A kind of vanadium cell, using the electrolyte diaphragm for vanadium cell as electrolyte membrance.
Embodiment 4
A kind of preparation method of electrolyte diaphragm for vanadium cell, includes the following steps:
1) preparation of quaternary silane: epoxychloropropane 14g is added in three-necked flask, slow with constant pressure funnel
Slow that bis- (diethylamino) silane 10g are added dropwise, in 58 DEG C of back flow reaction about 7.5h, revolving removes excessive epoxychloropropane,
Recrystallized 5 times in acetone, after again revolving remove acetone, obtain quaternary silane；
2) quaternary silane 14.4g, 4,4- dihydroxy two being prepared in step 1) preparation of polymer: will be passed through
Benzene sulfone 10g is dissolved in n,N-Dimethylformamide 110g, is waited after being completely dissolved, and catalyst 9g is added, in argon atmosphere, temperature is
Be stirred to react at 98 DEG C 7.5 hours, after settle out in acetone, and ethanol washing product 5 times are placed at 78 DEG C of vacuum oven
It dries 14 hours；The catalyst is benzyl dimethylamine, tetrabutylammonium bromide, benzyltriethylammoinium chloride 2:1:3 in mass ratio mixed
It closes；
3) preparation of diaphragm: polymer 10g, 1- allyl -3- vinyl imidazole bromine that will be prepared by step 2)
Salt 1g, the aqueous isopropanol 0.14g of chloroplatinic acid that mass fraction is 3% are dissolved in dimethyl sulfoxide 95g, ultrasound 14 minutes, after
Be stirred to react at 78 DEG C 1.8 hours, after be cast on mold, dried 14 hours in 88 DEG C of air dry oven, obtain diaphragm.
A kind of electrolyte diaphragm for vanadium cell is prepared using the preparation method of the vanadium cell electrolyte membrance.
A kind of vanadium cell, using the electrolyte diaphragm for vanadium cell as electrolyte membrance.
Embodiment 5
A kind of preparation method of electrolyte diaphragm for vanadium cell, includes the following steps:
1) preparation of quaternary silane: epoxychloropropane 15g is added in three-necked flask, slow with constant pressure funnel
Slow that bis- (diethylamino) silane 10g are added dropwise, in 60 DEG C of back flow reaction about 8h, revolving removes excessive epoxychloropropane, third
Recrystallized 5 times in ketone, after again revolving remove acetone, obtain quaternary silane；
2) quaternary silane 14.4g, 4,4- dihydroxy two being prepared in step 1) preparation of polymer: will be passed through
Benzene sulfone 10g is dissolved in n,N-Dimethylformamide 120g, is waited after being completely dissolved, and benzyltriethylammoinium chloride 10g is added, in nitrogen
Atmosphere, temperature are to be stirred to react 8 hours at 100 DEG C, after settle out in acetone, and it is dry to be placed on vacuum for ethanol washing product 5 times
It is dried 15 hours at 80 DEG C of dry case；
3) preparation of diaphragm: polymer 10g, 1- allyl -3- vinyl imidazole chlorine that will be prepared by step 2)
Salt 1g, the aqueous isopropanol 0.15g of chloroplatinic acid that mass fraction is 3% are dissolved in dimethyl sulfoxide 100g, ultrasound 15 minutes, after
Be stirred to react at 80 DEG C 2 hours, after be cast on mold, dried 15 hours in 90 DEG C of air dry oven, obtain diaphragm.
A kind of electrolyte diaphragm for vanadium cell is prepared using the preparation method of the vanadium cell electrolyte membrance.
A kind of vanadium cell, using the electrolyte diaphragm for vanadium cell as electrolyte membrance.
Comparative example
This example provides a kind of vanadium cell diaphragm, and raw material and formula are the same as Chinese invention patent CN107658478A embodiment
1。
Correlated performance test, test result such as 1 institute of table are carried out to sample film obtained by above-described embodiment 1-5 and comparative example
To show, test method is as follows,
(1) tensile strength is tested: being tested according to GB/T 1040-2006 " plastic tensile method for testing performance ".
(2 ionic conductivities: the impedance of the diaphragm of preparation is using two electrode AC impedance methods in electrochemical workstation
It is measured on (Zahner IM6EX), test frequency is 1Hz~1MHz.Ionic conductivity test is in the appearance for filling deionized water
It is measured in device, this is and to control temperature at 30 DEG C to guarantee that the relative humidity of film is 100%.It is tested in this temperature spot
Before, sample keeps constant temperature 30min at this temperature, and ionic conductivity is calculated according to following equation: σ=l/ (RS).
Wherein, σ is ionic conductivity (S cm-1), l is the distance between two electrodes (cm), and R hinders for the exchange of institute's sample
Anti-, S is the cross-sectional area of film.
(3) oxidation stability: film is dried into 5h at 60 DEG C, rapidly and its quality is accurately weighed, then, diaphragm is soaked
Steep the 0.1mol L at 40 DEG C-1VO2 ++3.0mol L-1H2SO4It is taken out after 20 hours in solution, washs, dries, measures diaphragm
Weight retention.Calculation formula are as follows: retention rate=(impregnating caudacoria weight-immersion cephacoria weight)/immersion cephacoria weight ×
100%.
(4) vanadium ion permeability: by the test reported in Journal ofPowe r Sources, 2012,217:309
Method test.
1 embodiment and comparative example sample membrane properties of table
As can be seen from the above table, vanadium cell Electrolyte Membranes disclosed by the embodiments of the present invention, with diaphragm in the prior art
Compare, there is more excellent tensile property and chemical stability, and its ionic conductivity with higher and lower vanadium from
Son infiltration, meets electrolyte diaphragm for vanadium cell requirement.
The basic principles, main features and advantages of the present invention have been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and what is described in the above embodiment and the description is only the present invention
Principle, various changes and improvements may be made to the invention without departing from the spirit and scope of the present invention, these variation and
Improvement is both fallen in the range of claimed invention.The present invention claims protection scope by appended claims and its
Equivalent defines.
Claims (9)
1. a kind of preparation method of electrolyte diaphragm for vanadium cell, which comprises the steps of:
1) preparation of quaternary silane: epoxychloropropane is added in three-necked flask, is slowly added dropwise with constant pressure funnel
Bis- (diethylamino) silane, in 50-60 DEG C of back flow reaction about 6-8h, revolving removes excessive epoxychloropropane, in acetone
Recrystallization 3-5 time, after again revolving removing acetone, obtain quaternary silane；
2) it the preparation of polymer: will be dissolved in by the quaternary silane, the 4,4- dihydroxydiphenylsulisomer that are prepared in step 1)
It in high boiling solvent, waits after being completely dissolved, catalyst is added, in nitrogen or atmosphere of inert gases, temperature is to stir at 90-100 DEG C
Mix reaction 6-8 hours, after settle out in acetone, and be placed at 60-80 DEG C of vacuum oven for ethanol washing product 3-5 times and dry
10-15 hours；
3) preparation of diaphragm: will divide by the polymer, 1- allyl -3- vinyl imidazole salt, quality that step 2) is prepared
Number is that the aqueous isopropanol of chloroplatinic acids of 2-3% is dissolved in dimethyl sulfoxide, 10-15 minute ultrasonic, after stirring is instead at 70-80 DEG C
Answer 1-2 hours, after be cast on mold, dried 10-15 hours in 80-90 DEG C of air dry oven, obtain diaphragm；
Wherein, the step 2) catalyst is selected from one of benzyl dimethylamine, tetrabutylammonium bromide, benzyltriethylammoinium chloride
Or it is several.
2. the preparation method of electrolyte diaphragm for vanadium cell according to claim 1, which is characterized in that described in step 1)
Epoxychloropropane, bis- (diethylamino) silane mass ratio be (1.2-1.5): 1.
3. the preparation method of electrolyte diaphragm for vanadium cell according to claim 1, which is characterized in that described in step 2)
Quaternary silane, 4,4- dihydroxydiphenylsulisomer, high boiling solvent, catalyst mass ratio be 1.44:1:(6-12): (0.5-
1)。
4. the preparation method of electrolyte diaphragm for vanadium cell according to claim 1, which is characterized in that the higher boiling is molten
Agent is selected from one or more of dimethyl sulfoxide, N,N-dimethylformamide, N-Methyl pyrrolidone.
5. the preparation method of electrolyte diaphragm for vanadium cell according to claim 1, which is characterized in that the inert gas
Selected from one or more of helium, neon, argon gas.
6. the preparation method of electrolyte diaphragm for vanadium cell according to claim 1, which is characterized in that described in step 3)
Polymer, 1- allyl -3- vinyl imidazole salt, the aqueous isopropanol of chloroplatinic acid, dimethyl sulfoxide mass ratio be (5-10): 1:
(0.1-0.15):(50-100)。
7. the preparation method of electrolyte diaphragm for vanadium cell according to claim 1, which is characterized in that the 1- allyl
Base -3- vinyl imidazole salt is in 1- allyl -3- vinyl imidazole villaumite, 1- allyl -3- vinyl imidazole bromide
It is one or more of.
8. a kind of vanadium that the preparation method using the described in any item vanadium cell electrolyte membrances of claim 1-7 is prepared electricity
Pond electrolyte membrance.
9. a kind of vanadium cell using electrolyte diaphragm for vanadium cell according to any one of claims 8 as electrolyte membrance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810287140.XA CN108598539B (en) | 2018-04-03 | 2018-04-03 | A kind of electrolyte diaphragm for vanadium cell and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810287140.XA CN108598539B (en) | 2018-04-03 | 2018-04-03 | A kind of electrolyte diaphragm for vanadium cell and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108598539A CN108598539A (en) | 2018-09-28 |
| CN108598539B true CN108598539B (en) | 2019-08-13 |
Family
ID=63624220
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810287140.XA Active CN108598539B (en) | 2018-04-03 | 2018-04-03 | A kind of electrolyte diaphragm for vanadium cell and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108598539B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114497900B (en) * | 2020-02-25 | 2023-09-22 | 江苏厚生新能源科技有限公司 | Lithium ion battery diaphragm with long cycle life and preparation method thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100540584C (en) * | 2004-06-29 | 2009-09-16 | 大日本油墨化学工业株式会社 | Aqueous dispersions of cationic polyurethane resins, contain its ink-jet accepting agent and the ink jet recording medium that uses it to make |
| CN102867971B (en) * | 2011-07-05 | 2014-10-22 | 中国科学院大连化学物理研究所 | Silane guanidine-based composite anionic membrane, its preparation and application |
| KR20130060159A (en) * | 2011-11-29 | 2013-06-07 | 롯데케미칼 주식회사 | Ion-exchange membbrane for redox flow batterry |
| JP6400577B2 (en) * | 2012-07-27 | 2018-10-03 | ロッキード マーティン エナジー, エルエルシーLockheed Martin Energy, Llc | Optimal membrane electrochemical energy storage system |
| WO2015057026A1 (en) * | 2013-10-18 | 2015-04-23 | 주식회사 엘지화학 | Ion transport material, electrolyte membrane comprising same, and method for producing same |
| KR101609649B1 (en) * | 2013-11-01 | 2016-04-06 | 한국에너지기술연구원 | Inorganic fiber reinforced organic-inorganic hybrid ion exchange membrane with high dimensional stability and high thermal resistance and method for manufacturing the same |
| WO2016089123A1 (en) * | 2014-12-02 | 2016-06-09 | 주식회사 엘지화학 | Polymer, method for manufacturing same, and electrolyte membrane comprising same |
-
2018
- 2018-04-03 CN CN201810287140.XA patent/CN108598539B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN108598539A (en) | 2018-09-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Gan et al. | Facile fabrication of amphoteric semi-interpenetrating network membranes for vanadium flow battery applications | |
| CN101891899B (en) | Ionic liquid doped heterocyclic polyarylether or sulfonate thereof for high-temperature and low-humidity ionic membrane and preparation method thereof | |
| CN106910922B (en) | Preparation method of amphoteric functional polyether-ether-ketone ion exchange membrane | |
| Chu et al. | Amphoteric membranes based on sulfonated polyether ether ketone and imidazolium‐functionalized polyphenylene oxide for vanadium redox flow battery applications | |
| Fang et al. | Novel anion exchange membranes based on pyridinium groups and fluoroacrylate for alkaline anion exchange membrane fuel cells | |
| CN108649255A (en) | Polybenzimidazoles proton exchange membrane and preparation method and application | |
| CN102867929B (en) | Composite anion-exchange membrane, its preparation and application | |
| JP2003123791A (en) | Proton conductor and fuel cell using the same | |
| CN108461790A (en) | A kind of long side chain SEBS bases alkaline polymer electrolyte membrane and its preparation and application | |
| CN108878936A (en) | A kind of hydrophobic side chain modification alkyl sulfonate polybenzimidazole amphoteric membrane and preparation method thereof | |
| CN107383404A (en) | A kind of preparation method of fluorine-containing branched sulphonated polyimides proton conductive membrane | |
| Chen et al. | Polybenzimidazole and polyvinylpyrrolidone blend membranes for vanadium flow battery | |
| CN105932317B (en) | A kind of preparation method of vanadium cell amberplex | |
| CN108598539B (en) | A kind of electrolyte diaphragm for vanadium cell and preparation method thereof | |
| Shi et al. | Long side-chain imidazolium functionalized poly (vinyl chloride) membranes with low cost and high performance for vanadium redox flow batteries | |
| CN107978779B (en) | Self-repairing anion exchange membrane for fuel cell and preparation method thereof | |
| CN101853947B (en) | Compound crosslinking alkaline polymer film for fuel cell, preparation method and application | |
| CN107978769B (en) | Triazine derivative-based diaphragm for vanadium battery and preparation method thereof | |
| CN110176617B (en) | Method for improving alcohol resistance selectivity of NAFION membrane | |
| CN103601888B (en) | Sulfonated polyarylethersulfoneand and blend membrane used for vanadium redox flow batteries and preparation method thereof | |
| CN108878740A (en) | A kind of non-ionic side chain modification polybenzimidazole membrane and preparation method thereof | |
| CN112421085B (en) | Perfluorosulfonic acid resin proton membrane for hydrogen fuel cell and preparation method thereof | |
| CN105375040B (en) | Electrode of liquid flow cell processing method | |
| CN111393695B (en) | Preparation method of self-crosslinking sulfonated polyimide membrane | |
| CN108676184B (en) | A kind of polymer anion-exchange membrane and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Zhou Luliu Inventor after: Other inventors request not to publish names Inventor before: The inventor has waived the right to be mentioned |
|
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20190718 Address after: Room 325, 46 Guangji Road, Lizhu Town, Keqiao District, Shaoxing City, Zhejiang Province Applicant after: Shaoxing Huahuo Intelligent Equipment Co., Ltd. Address before: 315040 501-516, B3 Floor, R&D Park, Ningbo High-tech Zone, Zhejiang Province Applicant before: NINGBO DIYANG ELECTRONIC TECHNOLOGY CO., LTD. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20201030 Address after: 118 Renmin East Road, Linjiang Town, Haimen District, Nantong City, Jiangsu Province, 226100 Patentee after: Nantong Jiangyong Investment Development Co., Ltd Address before: Room 325, 46 Guangji Road, Lizhu Town, Keqiao District, Shaoxing City, Zhejiang Province Patentee before: Shaoxing Huahuo Intelligent Equipment Co.,Ltd. |