CN109088098A - A kind of preparation method of single-ion polymer electrolyte membrance - Google Patents
A kind of preparation method of single-ion polymer electrolyte membrance Download PDFInfo
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- CN109088098A CN109088098A CN201810689336.1A CN201810689336A CN109088098A CN 109088098 A CN109088098 A CN 109088098A CN 201810689336 A CN201810689336 A CN 201810689336A CN 109088098 A CN109088098 A CN 109088098A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
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Abstract
The invention discloses a kind of preparation methods of single-ion polymer electrolyte membrance, it is formed a film in poly-vinyl alcohol solution using water-soluble mono ionomer, the single-ion polymer electrolyte membrance that ethyl alcohol is prepared as coagulating bath, the transport number of lithium ion can be effectively improved, while ionic conductivity, stability and mechanical performance are preferable.The single-ion polymer diaphragm of preparation does not have crystalline domain presence, effectively improves the porosity of diaphragm, while more unobstructed channel is also provided for lithium ion；Diaphragm porosity 87.82%, imbibition rate reach 88.46%；Tensile strength is 8.42Mpa；It is heated to 250 DEG C not shrink, and there is good flexibility；245 DEG C of thermal decomposition temperature, higher than the operating temperature of general lithium ion battery；The electrochemical stability window of diaphragm about 4.4V shows that the PVA-BAEE single-ion polymer electrolyte membrance of preparation of the embodiment of the present invention has good electrochemical stability, meets lithium ion battery to the electrochemical stability demand of diaphragm.
Description
Technical field
The invention belongs to technical field of lithium batteries, and in particular to a kind of preparation side of single-ion polymer electrolyte membrance
Method.
Background technique
Polymer dielectric tradition relatively uses for the lithium ion battery of polyalkene diaphragm, is able to suppress the life of Li dendrite
Length slows down working electrode volume discontinuities, improves the advantages such as battery security.But polymer dielectric be zwitterion simultaneously
Conduction, lithium ion transference number is lower, while ionic conductivity, stability and mechanical performance are lower.
Summary of the invention
In view of this, the embodiment provides a kind of transport number is higher, while ionic conductivity, stability and machine
The preparation method of the preferable single-ion polymer electrolyte membrance of tool performance.
Compared with the relevant technologies, technical solution used in the embodiment of the present invention is, a kind of single-ion polymer electrolyte every
The preparation method of film, comprising the following steps:
(1) single-ion polymer of (2- amino ethoxy) ethane of 1,2- bis- (BAEE) is prepared；
(2) take appropriate above-mentioned single-ion polymer in the methanol solution of lithium hydroxide, heating stirring obtains the list of lithiumation
Ionomer；
(3) it takes appropriate lithiumation single-ion polymer in polyvinyl alcohol (PVA) solution of degassing, is stood after heating stirring de-
Gas film forming；
(4) after forming a film film is put into dehydrated alcohol together together with glass plate, is taken out after it falls off naturally, remove table
The ethyl alcohol in face is dried to obtain single-ion polymer electrolyte membrance.
Preferably, in the step (1), the system of the single-ion polymer of 1,2- bis- (2- amino ethoxy) ethane (BAEE)
It is standby the following steps are included:
(1-1) prepares presoma 4,4 '-dicarboxyl dibenzenesulfonimide (CBSI)；Take suitable p-methylphenyl sulphonylamine and
P-methyl benzene sulfonic chloride is added in lithium hydroxide heating soluble in water by several times thereto after the completion of stirring, cooling is adjusted after the reaction was completed
PH value is saved, stands and concentrated hydrochloric acid generation precipitating is added in the filtrate of filtering, stand, filter at low temperature after filtering to take filter cake recrystallization
It is dried to obtain crude product；Crude product is reacted with potassium hydroxide, potassium permanganate, cold filtration, takes filtrate to be added after the reaction was completed
Filtration washing is stood after concentrated hydrochloric acid stirring, presoma CBSI is obtained after filtration cakes torrefaction；
(1-2) synthesizes single-ion polymer；Take the presoma CBSI, anhydrous lithium chloride of above-mentioned preparation in right amount in container,
Addition N-methyl pyrrolidones (NMP) after being passed through inert gas is vacuumized, sequentially adds (the 2- amino second of 1,2- bis- after rising temperature for dissolving
Oxygroup) ethane, triphenyl phosphite (TPP), pyridine (Py) reaction, sewage methanol is added after the reaction was completed, solid is precipitated；Use first
Alcohol filtration washing obtains single-ion polymer after obtaining filtration cakes torrefaction.
Preferably, in the step (2), heating temperature is 35 DEG C~45 DEG C, and mixing time is 22h~25h；The list of lithiumation
Stirring 22h~25h in anhydrous methanol is added in ionomer after filtration drying, filters to take filter cake in 95 DEG C~105 DEG C dryings
22h~25h obtains the single-ion polymer of lithiumation.
Preferably, in the step (3), heating temperature is 75 DEG C~85 DEG C, and mixing time is 6h~8h, stands degassing temperature
Degree is 55 DEG C~65 DEG C.
Preferably, in the step (4), drying temperature is 95 DEG C~105 DEG C, and the time is 22h~25h.
Preferably, in the step (1-1), p-methylphenyl sulphonylamine and lithium hydroxide are dissolved in 90 DEG C~95 DEG C water and adding
Heat, stirring to solution clear；Addition p-methyl benzene sulfonic chloride reaction 12~for 24 hours, using dilute after being cooled to 40 DEG C~50 DEG C
Salt acid for adjusting pH value is neutrality；It is stood after filter cake recrystallization at 1 DEG C~5 DEG C, crude product and potassium hydroxide rear gradation soluble in water
Potassium permanganate is added in 90 DEG C~95 DEG C reaction 12h~for 24 hours, after the reaction was completed cold filtration, 40 DEG C of concentrated hydrochloric acid of filtrate addition~
45 DEG C of stirring 6h~8h filterings, 95 DEG C in a vacuum drying oven~105 DEG C dryings of filter cake are for 24 hours.
Preferably, in the step (1-2), N-methyl pyrrolidones is added and is warming up to 90 DEG C~95 DEG C dissolutions, is added 1,
It is transparent that 2- bis- (2- amino ethoxy) ethane, triphenyl phosphite (TPP), pyridine (Py), which react 12h~14h to reaction solution,
Shape；Dry single-ion polymer for 24 hours at 95 DEG C in a vacuum drying oven~105 DEG C of filter cake.
Single-ion polymer electrolyte membrance is prepared according to the method for the embodiment of the present invention, surface is tufted knot
Structure, the gap between tufted structure are 4 μm~6 μm；Porosity is 85%~90%, and imbibition rate is 85%~90%.
Preferably, the tensile strength of the single-ion polymer electrolyte membrance is 8.35Mpa~8.45Mpa, thermal decomposition
Temperature is 240 DEG C~250 DEG C.
The technical solution that the embodiment of the present invention provides has the benefit that single-ion polymer electrolysis of the invention
The preparation method of matter diaphragm, preparation method is simple, is formed a film in poly-vinyl alcohol solution using water-soluble mono ionomer, ethyl alcohol
As the single-ion polymer electrolyte membrance that coagulating bath is prepared, the transport number of lithium ion, while ion can be effectively improved
Conductivity, stability and mechanical performance are preferable.
Detailed description of the invention
Fig. 1 is the preparation method flow chart of the embodiment of the present invention；
Fig. 2 is the infrared spectrogram of the single-ion polymer of preparation of the embodiment of the present invention；
Fig. 3 is the nmr spectrum of the single-ion polymer of preparation of the embodiment of the present invention；
Fig. 4 a is the single-ion polymer electrolyte membrance surface scan electron microscope of preparation of the embodiment of the present invention；
Fig. 4 b is the single-ion polymer electrolyte membrance profile scanning electron microscope of preparation of the embodiment of the present invention；
Fig. 5 is the single-ion polymer electrolyte membrance of the embodiment of the present invention and the DSC curve figure of PP film；
Fig. 6 is the single-ion polymer electrolyte membrance anti-flammability test chart of the embodiment of the present invention；
Fig. 7 is the single-ion polymer electrolyte membrance and PP film thermal contraction test figure of the embodiment of the present invention；
Fig. 8 is the single-ion polymer electrolyte membrance and PP film thermogravimetric analysis figure of the embodiment of the present invention；
Fig. 9 is the single-ion polymer electrolyte membrance electrochemical stability window schematic diagram of the embodiment of the present invention；
Figure 10 is the synthetic reaction schematic diagram of the single-ion polymer BAEE of the embodiment of the present invention.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with attached drawing to embodiment party of the present invention
Formula is further described.
Referring to FIG. 1, the embodiment provides a kind of preparation method of single-ion polymer electrolyte membrance, packet
Include following steps:
(1) single-ion polymer of (2- amino ethoxy) ethane of 1,2- bis- (BAEE) is prepared；
Specifically, the preparation of the single-ion polymer of (2- amino ethoxy) ethane of 1,2- bis- (BAEE) includes following step
It is rapid:
(1-1) prepares presoma 4,4 '-dicarboxyl dibenzenesulfonimide (CBSI)；Take suitable p-methylphenyl sulphonylamine and
Lithium hydroxide is dissolved in 90 DEG C~95 DEG C of water, and p-methyl benzene sulfonic chloride is added after stirring to solution clear by several times thereto
Reaction 12~for 24 hours, it is cooled to 40 DEG C~50 DEG C adjusting pH value after the reaction was completed as neutrality, stands and dense salt is added in the filtrate of filtering
Acid generates precipitating, stands in a low temperature of 1 DEG C~5 DEG C after filtering to take filter cake recrystallization, filtration drying obtains crude product；It will slightly produce
The gradation soluble in water of object and potassium hydroxide is added 90 DEG C~95 DEG C of potassium permanganate and reacts 12h~for 24 hours, cooled after the reaction was completed
Filter takes filtrate that concentrated hydrochloric acid is added and stir 6h~8h standing filtration washing, filter cake in a vacuum drying oven 95 at 40 DEG C~45 DEG C
DEG C~105 DEG C of dryings obtain presoma CBSI for 24 hours；
(1-2) synthesizes single-ion polymer；Take the presoma CBSI, anhydrous lithium chloride of above-mentioned preparation in right amount in container,
Addition N-methyl pyrrolidones (NMP) after being passed through inert gas is vacuumized, sequentially adds 1,2- after 90 DEG C~95 DEG C dissolutions that heat up
Two (2- amino ethoxy) ethane, triphenyl phosphite (TPP), pyridine (Py) react 12h~14h, and nothing is added after the reaction was completed
Solid is precipitated in water methanol；With methanol filtration washing obtain in filter cake vacuum oven at 95 DEG C~105 DEG C it is dry obtain for 24 hours it is isolated
Sub- polymer；
Referring to attached drawing 2,3, there is the characteristic absorption peak of carboxyl, amino and ehter bond in infrared spectroscopy；Hydrogen nuclear magnetic resonance
Occur the characteristic absorption peak of amide group hydrogen in spectrum, it is water-soluble isolated to show that the method for the embodiment of the present invention is successfully prepared
Sub- polymer；
(2) take appropriate above-mentioned single-ion polymer in the methanol solution of lithium hydroxide, heating stirring at 35 DEG C~45 DEG C
22h~25h obtains the single-ion polymer of lithiumation；
Specifically, stirring 22h~25h in anhydrous methanol, filtering is added in the single-ion polymer of lithiumation after filtration drying
It takes filter cake in 95 DEG C~105 DEG C dry 22h~25h, obtains the single-ion polymer of lithiumation；
(3) it takes appropriate lithiumation single-ion polymer in polyvinyl alcohol (PVA) solution of degassing, is heated at 75 DEG C~85 DEG C
Degassing film forming is stood after stirring 6h~8h；
(4) after forming a film film is put into dehydrated alcohol together together with glass plate, is taken out after it falls off naturally, remove table
The ethyl alcohol in face, dry 22h~25h obtains single-ion polymer electrolyte membrance at 95 DEG C~105 DEG C.
Single-ion polymer electrolyte membrance is prepared according to the method for the embodiment of the present invention, surface is tufted knot
Structure, the gap between tufted structure are 4 μm~6 μm；Porosity is 85%~90%, and porosity height is conducive to improve ionic conductance
Rate has good permeability to lithium ion to reduce the internal resistance of cell；Imbibition rate is 85%~90%, is had more to electrolyte
Good adsorptivity, reduces the internal resistance of cell to a certain extent；The tensile strength of the single-ion polymer electrolyte membrance is
8.35Mpa~8.45Mpa is not easy the deformation that is stretched during the manufacturing of diaphragm, while also improving the safety of battery
Property；Thermal decomposition temperature is 240 DEG C~250 DEG C.
Referring to attached drawing 4a, 4b, single-ion polymer electrolyte membrance surface is at uneven irregular tufted structure, tufted
There are gaps between structure, and gap size is about at 5 μm or so；By sectional view it is found that diaphragm has preferable compactness, tufted knot
The gap of structure not will lead to film and run through.
Referring to attached drawing 5, PP film shows that there are certain crystalline domains inside PP film macromolecule there are two exothermic peaks；And
Crystalline domain can reduce the porosity of diaphragm, lithium ion mobility be hindered, to increase the internal resistance of cell.And PVA-BAEE single ion
Endothermic peak is not present in polymer electrolyte diaphragm, shows that the macromolecule for forming diaphragm does not have crystalline domain presence, effectively improves
The porosity of diaphragm, while also providing more unobstructed channel for lithium ion.
Referring to attached drawing 6,7, can be shunk immediately after flame, when flame is close, diaphragm shrinks and is carbonized, will not
It burns immediately, the flame retardant property of single-ion polymer electrolyte membrance is preferable.
Referring to attached drawing 7, left side is PP film in figure, and right side is the PVA-BAEE single-ion polymer of preparation of the embodiment of the present invention
Electrolyte membrance still is able to keep integrity of shape after temperature reaches 250 DEG C.Show PVA-BAEE single-ion polymer electricity
Solution matter has good dimensional stability, is not susceptible to shrink after heated, not will lead to pole piece leakage and makes battery short circuit, guarantees
Also it can be improved the operating temperature of battery while cell safety.
Referring to attached drawing 8, single-ion polymer electrolyte membrance (the PVA-BAEE polymer electrolytic of preparation of the embodiment of the present invention
Matter diaphragm) quality weightless very little before 245 DEG C, there is apparent weight loss at 245 DEG C or so, can determine that it decomposes temperature
Degree 245 DEG C near, much higher than general lithium ion battery operating temperature, it is heated under normal circumstances to be not susceptible to point
Solution.
Referring to attached drawing 9, the operating voltage of conventional lithium ion battery generally in 3.8V or so, PVA-BAEE electrolyte membrance
Electrochemically stable voltage is 4.4V or so, shows that polymer electrolyte diaphragm has preferable electrochemical stability, can satisfy
Redox reaction will not occur under lithium ion battery normal working voltage, can make extensively in the battery of general anode material
With.
Embodiment two
The embodiment provides a kind of preparation methods of single-ion polymer electrolyte membrance, including following step
It is rapid:
(1) single-ion polymer of (2- amino ethoxy) ethane of 1,2- bis- (BAEE) is prepared；
Specifically, the preparation of the single-ion polymer of 1,2-, bis- (2- amino ethoxy) ethane (BAEE) includes following
Step:
(1-1) prepares presoma 4,4 '-dicarboxyl dibenzenesulfonimide (CBSI)；Wherein this sulfonamide of 4- methyl, 4- first
The ratio of the amount of the substance of base benzene sulfonyl chloride is 2:1；P-methylphenyl sulphonylamine and LiOH are dissolved at 95 DEG C with suitable quantity of water, stirred
P-methyl benzene sulfonic chloride is added after to clear several times on a small quantity, reaction is overnight；45 DEG C are cooled to, adjusts pH=with dilute hydrochloric acid
7.0, it stands overnight；The filtrate of filtering is added dropwise to concentrated hydrochloric acid and is generated without precipitating；The filter cake of filtering is heated with a large amount of water and is recrystallized,
It is put into refrigerator overnight, filtration drying, as crude product；Crude product, potassium hydroxide, potassium permanganate are aoxidized according to 1:1:5
Primary product and potassium hydroxide are added appropriate ultrapure water and dissolved, potassium permanganate be added several times on a small quantity, 95 DEG C were reacted by reaction
Night；Cooled and filtered, filtrate are precipitated with a large amount of concentrated hydrochloric acids, stir 6h at 40 DEG C, wash twice, filtering, and air dry oven is dry；
It is dried for 24 hours at 100 DEG C in vacuum oven after grinding；Synthetic reaction formula is as follows:
The synthesis of (1-2) single-ion polymer BAEE；Wherein 1,2 bis- (2- amino ethoxy) ethane, 4,4 '-dicarboxyls
Dibenzenesulfonimide (CBSI) the mass ratio of the material is 1:1；Reaction carries out under the protection of anhydrous and oxygen-free argon gas；A certain amount of 4 are weighed,
Magneton is added in flask in 4 '-dicarboxyl dibenzenesulfonimide (CBSI) solids, anhydrous lithium chloride；It vacuumizes, is filled with argon gas；
N-methyl pyrrolidones (NMP) is added with syringe, being warming up to 95 DEG C dissolves solid.1,2 pairs are sequentially added after solid dissolution
(2- amino ethoxy) ethane, triphenyl phosphite (TPP), pyridine (Py)；Reactant, solvent etc. should be reduced during this to the greatest extent
The time contacted with air prevents its water suction, oxidation；After reacting 12h, reaction solution is transparence.It is added in reaction solution a large amount of
Anhydrous methanol, make white solid all be precipitated；Filtering, is washed with methanol, and filter cake is transferred in culture dish, in air dry oven just
Drying is walked, after taking-up grinding for 24 hours with drying at 100 DEG C of vacuum oven；It is closed after drying, it is saved in drier；Synthesis is anti-
Answer formula as shown in Figure 10:
(2) take above-mentioned single-ion polymer in 500mL 0.5molL-1LiOH methanol solution in, stirred at 40 DEG C
For 24 hours, make polymer single ion BAEE lithiumation, filter, air dry oven is dry；Since lithium hydroxide is easy to be precipitated in methyl alcohol,
The single-ion polymer after lithiumation is added in 500 mL anhydrous methanols again after dry and is stirred for 24 hours, lithiumation process is dissolved
The LiOH solid of middle precipitation；Filtering is ground after air dry oven preliminarily dried, and 100 DEG C of dryings are for 24 hours in vacuum oven.It is dry
It is closed afterwards, it is saved in drier；
(3) 10% PVA solution that mass fraction is is prepared first: a certain amount of PVA is stirred at 90 DEG C with aqueous solvent
Mix dissolution, stand degassing, take appropriate lithiumation single-ion polymer in polyvinyl alcohol (PVA) solution of degassing, PVA with it is isolated
Sub- polymer quality ratio is 1:1, is vigorously stirred 6~8h at 80 DEG C and makes it dissolve, 60 DEG C of standing degassings, in glass plate after cooling
Upper curtain coating automatic coating machine film forming；
(4) after forming a film film is put into dehydrated alcohol immediately together together with glass plate, takes out, removes after it falls off naturally
The ethyl alcohol for going to surface is dried to obtain single-ion polymer electrolyte membrance.Remaining is the same as embodiment one.
The single-ion polymer electrolyte membrance prepared according to the method for the embodiment of the present invention, surface are tufted structure,
Gap between tufted structure is 5 μm；Porosity is 87.82%；Imbibition rate is 88.46%；The single-ion polymer electrolysis
The tensile strength of matter diaphragm is 8.42Mpa；Thermal decomposition temperature is 245 DEG C.
Herein, the nouns of locality such as related front, rear, top, and bottom are to be located in figure with components in attached drawing and zero
Part mutual position defines, only for the purpose of expressing the technical solution clearly and conveniently.It should be appreciated that the noun of locality
Use should not limit the claimed range of the application.
In the absence of conflict, the feature in embodiment and embodiment herein-above set forth can be combined with each other.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of preparation method of single-ion polymer electrolyte membrance, characterized in that the following steps are included:
(1) single-ion polymer of (2- amino ethoxy) ethane of 1,2- bis- (BAEE) is prepared；
(2) take appropriate above-mentioned single-ion polymer in the methanol solution of lithium hydroxide, heating stirring obtains the single ion of lithiumation
Polymer；
(3) take appropriate lithiumation single-ion polymer in polyvinyl alcohol (PVA) solution of degassing, after heating stirring stand degassing at
Film；
(4) after forming a film film is put into dehydrated alcohol together together with glass plate, is taken out after it falls off naturally, removes surface
Ethyl alcohol is dried to obtain single-ion polymer electrolyte membrance.
2. a kind of preparation method of single-ion polymer electrolyte membrance according to claim 1, characterized in that the step
Suddenly in (1), the preparation of the single-ion polymer of 1,2- bis- (2- amino ethoxy) ethane (BAEE) the following steps are included:
(1-1) prepares presoma 4,4 '-dicarboxyl dibenzenesulfonimide (CBSI)；Take suitable p-methylphenyl sulphonylamine and hydrogen-oxygen
Change lithium heating soluble in water, p-methyl benzene sulfonic chloride is added after the completion of stirring by several times thereto, cooling adjusts pH after the reaction was completed
Value stands and concentrated hydrochloric acid generation precipitating is added in the filtrate of filtering, stands at low temperature after filtering to take filter cake recrystallization, filtration drying
Obtain crude product；Crude product is reacted, after the reaction was completed cold filtration with potassium hydroxide, potassium permanganate, takes filtrate that dense salt is added
Filtration washing is stood after acid stirring, presoma CBSI is obtained after filtration cakes torrefaction；
(1-2) synthesizes single-ion polymer；It takes the presoma CBSI, anhydrous lithium chloride of above-mentioned preparation in right amount in container, takes out true
N-methyl pyrrolidones (NMP) is added after being passed through inert gas in sky, sequentially adds (the 2- amino ethoxy of 1,2- bis- after rising temperature for dissolving
Base) ethane, triphenyl phosphite (TPP), pyridine (Py) reaction, sewage methanol is added after the reaction was completed, solid is precipitated；Use methanol
Filtration washing obtains single-ion polymer after obtaining filtration cakes torrefaction.
3. a kind of preparation method of single-ion polymer electrolyte membrance according to claim 2, characterized in that the step
Suddenly in (1-1), p-methylphenyl sulphonylamine and lithium hydroxide are dissolved in 90 DEG C~95 DEG C water and heating, stirring to solution clear；
Addition p-methyl benzene sulfonic chloride reaction 12~for 24 hours, use dilute hydrochloric acid to adjust pH value as neutrality after being cooled to 40 DEG C~50 DEG C；Filter cake
It is stood after recrystallization at 1 DEG C~5 DEG C, crude product and the potassium hydroxide rear potassium permanganate that is added by several times soluble in water are at 90 DEG C~95 DEG C
Reaction 12h~for 24 hours, 40 DEG C~45 DEG C stirring 6h~8h filterings of concentrated hydrochloric acid are added in cold filtration, filtrate after the reaction was completed, and filter cake exists
95 DEG C~105 DEG C dryings are for 24 hours in vacuum oven.
4. a kind of preparation method of single-ion polymer electrolyte membrance according to claim 2, characterized in that the step
Suddenly in (1-2), N-methyl pyrrolidones is added and is warming up to 90 DEG C~95 DEG C dissolutions, 1,2- bis- (2- amino ethoxy) second is added
Alkane, triphenyl phosphite (TPP), pyridine (Py) reaction 12h~14h to reaction solution are transparence；Filter cake is in a vacuum drying oven
Dry single-ion polymer for 24 hours at 95 DEG C~105 DEG C.
5. a kind of preparation method of single-ion polymer electrolyte membrance according to claim 1, characterized in that the step
Suddenly in (2), heating temperature is 35 DEG C~45 DEG C, and mixing time is 22h~25h；The single-ion polymer of lithiumation is through filtration drying
It is added in anhydrous methanol afterwards and stirs 22h~25h, filter to take filter cake in 95 DEG C~105 DEG C dry 22h~25h, obtain the list of lithiumation
Ionomer.
6. a kind of preparation method of single-ion polymer electrolyte membrance according to claim 1, characterized in that, it is described
In step (3), heating temperature is 75 DEG C~85 DEG C, and mixing time is 6h~8h, and standing degassing temperature is 55 DEG C~65 DEG C.
7. a kind of preparation method of single-ion polymer electrolyte membrance according to claim 2, characterized in that the step
Suddenly in (4), drying temperature is 95 DEG C~105 DEG C, and the time is 22h~25h.
8. a kind of single-ion polymer electrolyte membrance, characterized in that the single-ion polymer electrolyte membrance, surface is
Tufted structure, the gap between tufted structure are 4 μm~6 μm；Porosity is 85%~90%, and imbibition rate is 85%~90%.
9. a kind of single-ion polymer electrolyte membrance according to claim 8, characterized in that the single-ion polymer
The tensile strength of electrolyte membrance is 8.35Mpa~8.45Mpa, and thermal decomposition temperature is 240 DEG C~250 DEG C.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113991172A (en) * | 2021-09-30 | 2022-01-28 | 中国地质大学（武汉） | Linear single-ion conductive polymer electrolyte PECB and preparation method and application thereof |
| CN114539451A (en) * | 2022-03-09 | 2022-05-27 | 中国地质大学（武汉） | Hydroxyl-rich single-ion conductor polymer SPVA-Li and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014022224A1 (en) * | 2012-08-02 | 2014-02-06 | The Penn State Research Foundation | Polymer conductor for lithium-ion batteries |
| CN104183869A (en) * | 2014-08-25 | 2014-12-03 | 江苏明魁高分子材料技术有限公司 | Lithium single ionic conductive microporous electrolyte membrane and preparation method thereof |
-
2018
- 2018-06-28 CN CN201810689336.1A patent/CN109088098B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014022224A1 (en) * | 2012-08-02 | 2014-02-06 | The Penn State Research Foundation | Polymer conductor for lithium-ion batteries |
| CN104183869A (en) * | 2014-08-25 | 2014-12-03 | 江苏明魁高分子材料技术有限公司 | Lithium single ionic conductive microporous electrolyte membrane and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 张运丰: "单离子聚合物电解质的设计、合成及在锂离子电池中的应用", 《中国地质大学博士学位论文》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113991172A (en) * | 2021-09-30 | 2022-01-28 | 中国地质大学（武汉） | Linear single-ion conductive polymer electrolyte PECB and preparation method and application thereof |
| CN113991172B (en) * | 2021-09-30 | 2024-01-30 | 中国地质大学（武汉） | Linear single ion conductive polymer electrolyte PECB, preparation method and application thereof |
| CN114539451A (en) * | 2022-03-09 | 2022-05-27 | 中国地质大学（武汉） | Hydroxyl-rich single-ion conductor polymer SPVA-Li and preparation method and application thereof |
| CN114539451B (en) * | 2022-03-09 | 2022-11-08 | 中国地质大学（武汉） | Hydroxyl-rich single-ion conductor polymer SPVA-Li and preparation method and application thereof |
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