CN105489940B - A kind of method that simplicity prepares lithium ionic cell polymer electrolyte film - Google Patents
A kind of method that simplicity prepares lithium ionic cell polymer electrolyte film Download PDFInfo
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- CN105489940B CN105489940B CN201510542908.XA CN201510542908A CN105489940B CN 105489940 B CN105489940 B CN 105489940B CN 201510542908 A CN201510542908 A CN 201510542908A CN 105489940 B CN105489940 B CN 105489940B
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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
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
A kind of method that simplicity prepares big specification lithium ionic cell polymer electrolyte film.It is related to a kind of preparation method of lithium ionic cell polymer electrolyte film.Present invention mainly solves electrolyte in existing commercial battery leakage problem and security risk and the relatively low electrical conductivity of all solid state electrolyte film the problem of.The preparation method of the present invention is as follows：By 0.5g PVdF be dissolved in 2 3ml DMF solvents 15 it is small when, by 2wt% 6wt%MMT be dissolved in 1 2ml THF solvents 15 it is small when, be further continued for after the two mixing stirring 15 it is small when；The solution being stirred is ultrasonically treated 5 10 minutes, again by 0.1g PVA be dissolved in 1 2ml DMF solvents 2 it is small when, solution with being mixed with PVdF and MMT continues to mix, add appropriate lithium salts and continue stirring 6 it is small when, the Polymer Solution being stirred is poured on the glass plate of cleaning, glass plate is put into vacuum drying chamber and carries out drying and processing, 120 DEG C of heating-up temperature, takes out after time 60min clock stand-by.The present invention is applied to field of lithium ion battery.
Description
Technical field
The present invention relates to a kind of method that simplicity prepares big specification lithium ionic cell polymer electrolyte film.
Background technology
With expanding economy and the progress of civilization, sustainable, environment is increasingly tended in dependence of the mankind for the energy
Friendly new energy system.Lithium ion battery is born at the end of the 20th century, is a kind of green high-capacity environment-protecting type battery, with its work electricity
Pressure is high, bigger than energy, have extended cycle life, pollutes the advantages that small shows one's talent in numerous electrochmical power sources, from 20th century 90
Receive much concern since age commercialization because of its superior performance, become the mainstream electrical source of power of pure electric vehicle EV and hybrid power HEV
One of.However, the presence of organic electrolyte can cause many safety problems, and then restrict its development, in high temperature, short circuit, overcharge
When putting, extrude and hitting, easily occur smoldering, catch fire or even the phenomenon of explosion, thus can not meet very well EV and
The practical needs of HEV.Polymer dielectric to avoid the leakage problem of conventional liquid lithium ion battery, can improve the peace of battery
Full performance and energy density, and can realize the thinning, lighting and shape variability of battery.And easy to operate, polymer electrolytic
Matter is closed extensively in fields such as battery, fuel sensitization solar battery, ultracapacitor, chemical sensor and electrochromism
Note.Many polymeric systems be used to study the mechanism of action of the solid solvent to ion, but solid polymer is electric up to now
Solution matter still cannot meet the needs of industrialization large-scale production；Low cost makes polymer film electrolyte become lithium ion battery
One of most potential material in manufacture.
Casting method is that one kind uses extensively, easy to operate, can obtain high quality, the forming method of ideal dimensions membrane.
Casting method is that the components such as macromolecule matrix, lithium salts, inorganic particulate are added in solvent, and be uniformly mixed stable slurry,
Cast on clean smooth glass plate or polytetrafluoroethylene (PTFE), obtain evenly laid out, the liquid layer of property stable homogeneous, vacuum
Drying finally obtains polymer dielectric film until the volatilization of complete solvent.The method equipment is simple, easy to operation, production effect
Rate is high, process stabilizing therefore the material in membrane are prepared with being widely used in moulding process.
The content of the invention
The purpose of the present invention is to solve lithium-ion battery electrolytes leakage problem and solid electrolyte membrane conductivity not
The problems such as preferable, the present invention provide a kind of method for preparing PVdF/PVA/MMT solid polymer electrolyte films.
The method for preparing PVdF/PVA/MMT solid polymer electrolyte films of the present invention,
It includes the following steps.
Step 1：By stand-by PVdF, PVA is positioned over drying box drying process.
Step 2：By 0.5g PVdF be dissolved in 2-3ml DMF solvents 15 it is small when, 2wt %-6wt %MMT are dissolved in 1-2ml
It is further continued for ensureing that Polymer Solution is uniform and stable when stirring 15 is small when THF solvents 15 are small, after the two mixing.
Step 3：The solution being stirred is ultrasonically treated 5-10 minutes.
Step 4：First by 0.1g PVA be dissolved in 1-2ml DMF solvents 2 it is small when, be mixed with PVdF and MMT solution continue
Mixing, add appropriate lithium salts and continue stirring 6 it is small when until solution it is uniform and stable.
Step 5：Repeat step three, then performs step 6.
Step 6：The Polymer Solution being stirred is poured on the glass plate of cleaning, according to different width and thickness
Need, be fabricated to the paper slip of different-thickness, outsourcing adhesive tape, sets horizontal width, fixes on a glass, makes simple
Model, then casting are placed after obtaining the homogeneous liquid layer of thickness until occurring without bubble.
Step 7：Glass plate is put into vacuum drying chamber and carries out drying and processing, 120 DEG C of heating-up temperature, after time 60min clock
Take out stand-by.Before vacuum drying, phosphorus pentoxide is placed in drying box, to absorb the solvent steamed without damaging drying
Case.Film is washed into the identical disk of size with the sheet-punching machine of 14mm, in case being used during packed battery.
The advantage of the invention is that：Long agitation can make polymer P VdF, PVA dissolving fully, and MMT is substantially inserted into
In PVdF matrixes, the thin and thick of obtained film and specification are easy to control, and preparation method is simple and convenient, and obtained film mechanical performance is good
Good, chemical property is more satisfactory, and thin and thick is uniform, has good physical appearance, and cost is relatively low.
Brief description of the drawings
Fig. 1 is the SEM schematic diagrames of PVdF/PVA in embodiment one of the invention.
Fig. 2 is the SEM schematic diagrames of PVdF/PVA/MMT films in embodiment one of the invention.
Fig. 3 is the AFM schematic diagrames at 90 ° of visual angles of PVdF/PVA films in embodiment one of the invention.
Fig. 4 is the AFM schematic diagrames at 90 ° of visual angles of PVdF/PVA/MMT films in embodiment one of the invention.
Fig. 5 be the present invention embodiment one in PVdF/PVA/MMT films tensile stress test chart, abscissa
For displacement, ordinate is load.
Fig. 6 is the thermogravimetric analysis figure of PVdF/PVA/MMT films in embodiment one of the invention, and abscissa is temperature
Degree, ordinate is weight-loss ratio.
Fig. 7 is the linear voltammetric scan that PVdF/PVA/MMT films are assembled into battery in embodiment one of the invention
Figure, abscissa is current potential, and ordinate is electric current.
Fig. 8 is the cyclic voltammogram that PVdF/PVA/MMT films are assembled into battery in embodiment one of the invention,
Abscissa is current potential, and ordinate is electric current.
Fig. 9 is assembled into the impedance diagram of battery, horizontal seat for PVdF/PVA/MMT films in the embodiment one of the present invention
Impedance real part is designated as, ordinate is imaginary impedance.
Figure 10 is the charge and discharge electrograph that PVdF/PVA/MMT films are assembled into battery in embodiment one of the invention, horizontal
Coordinate is cycle-index, and ordinate is specific discharge capacity.
Embodiment
Embodiment one：Preparation PVdF/PVA/MMT solid polymer electrolyte films described in present embodiment
Method, the method for preparing PVdF/PVA/MMT solid polymer electrolyte films,
It includes the following steps.
Step 1：By stand-by PVdF, PVA is positioned over drying box drying process.
Step 2：By 0.5g PVdF be dissolved in 2-3ml DMF solvents 15 it is small when, 2wt%-6wt% MMT are dissolved in 1-2ml
When THF solvents 15 are small, the two mixing is further continued for ensureing that Polymer Solution is uniform and stable when stirring 15 is small.
Step 3：The solution being stirred is ultrasonically treated 5-10 minutes.
Step 4：In advance by 0.1g PVA be dissolved in 1-2ml DMF solvents 2 it is small when, be mixed with PVdF and MMT solution continue
Mixing, add appropriate lithium salts and continue stirring 6 it is small when until solution it is uniform and stable.
Step 5：Repeat step three, then performs step 6.
Step 6：The Polymer Solution being stirred is poured on the glass plate of cleaning, the Polymer Solution that will be stirred
It is poured on the glass plate of cleaning, according to different width and thickness needs, is fabricated to the paper slip of different-thickness, outsourcing transparent adhesive tape
Band, sets horizontal width, fixed to make simple model on a glass, and then casting is put after obtaining the homogeneous liquid layer of thickness
Put until occurring without bubble.
Step 7：Glass plate is put into vacuum drying chamber and carries out drying and processing, 120 DEG C of heating-up temperature, after time 60min clock
Take out stand-by.Before vacuum drying, phosphorus pentoxide is placed in drying box, to absorb the solvent steamed without damaging drying
Case.Film is washed into the identical disk of size with the sheet-punching machine of 14mm, in case being used during packed battery.
Present embodiment carries out in measuring cup, avoids the impurity foul solution in air；
Good electrochemical stability, good electrolyte compatibility, outstanding mechanical performance cause PVdF to be well suited for using
To prepare lithium ion battery separator.In addition, PVdF also has higher dielectric constant and relatively low glass transition temperature, favorably
In the dissociation of lithium salts, the carrier number in polymer electrolyte system is improved.Therefore PVdF is to prepare gel electrolyte relatively to manage
The polymer thought.But the presence of crystalline region limits the conduction of ion in PVdF, it is therefore desirable to it is modified, due to PVA
Molecule contains compared with long-chain branch, has good compliance, and glass transition temperature is low, there is very high stretching and impact strength, can be with
By PVA blendings in PVdF, polymer regularity is destroyed, to improve the conductivity of lithium-ion electrolyte film.
The volatilization in addition, inorganic salts material can be heated during polymerization, by duct number and diameter increase, intercalation is made
With and pore-creating effect all be beneficial to lithium ion migration, in addition, the addition of inorganic particulate also destroys the order degree of polymer, make
Degree of disorder increase, so that the electrical conductivity of bigger and more excellent electrochemical properties are obtained, so we choose common nanometer
Grain, montmorillonite is as addition particle.
The film microscopic appearance figure for adding as can be seen from comparison with Figure 1 and Figure 2 and not adding montmorillonite particle, using this reality
The addition montmorillonite particle in mode is applied, film porosity and aperture are more preferable.
Can be with it is further seen that addition and the film microscopic appearance for not adding montmorillonite particle, be implemented with this from Fig. 3 and Fig. 4
Addition montmorillonite particle in mode, film is from spatially seeing that porosity and aperture are more preferable.
Can be with it is further seen that after addition montmorillonite particle, the tensile resistance enhancing of film, mechanical performance obtains from Fig. 5
Improve.
Conclusion as can be drawn from Figure 6, adds the film decomposition temperature rise of montmorillonite particle, and weight-loss ratio reduces, heating power
Performance is learned to greatly improve.
Maximum tension in present embodiment using the polymer electrolyte film of the addition montmorillonite particle of step 3 is strong
Degree is up to 2.24MPa.
Embodiment two：Present embodiment is that the preparation PVdF/PVA/MMT described in embodiment one is consolidated
The further explanation of the method for body polymer electrolyte film, the step 2 are：By dried PVdF and MMT in step 1
Stirring 15h is remixed to ensure solution stable homogeneous after when being dissolved in appropriate DMF and small THF solution stirring 15 respectively.
Embodiment three：Present embodiment is that the preparation PVdF/PVA/MMT described in embodiment one is consolidated
The further explanation of the method for body polymer electrolyte film,
The step 3 is：The Polymer Solution being stirred in step 2 is put in ultrasound and vibrates 5-10min, is ensured molten
The homogeneity of liquid.
Embodiment four：Present embodiment is that the preparation PVdF/PVA/MMT described in embodiment one is consolidated
The further explanation of the method for body polymer electrolyte film, the step 4 are：It is molten that 0.1g PVA are first dissolved in 1-2ml DMF
When agent 2 is small, the solution with being mixed with PVdF and MMT continues to mix, add appropriate lithium salts and continue stirring 6 it is small when until homogeneous steady
It is fixed.
Embodiment five:Present embodiment is that the preparation PVdF/PVA/MMT described in embodiment one is consolidated
The further explanation of the method for body polymer electrolyte film,
The mixed uniformly solution of step 4 kind is put into ultrasound and is vibrated, repeat step three, then performs step 6.
Embodiment six：Present embodiment is that the preparation PVdF/PVA/MMT described in embodiment one is consolidated
The Polymer Solution being stirred, is poured in the step 6 clean by the further explanation of the method for body polymer electrolyte film
On net glass plate, the Polymer Solution being stirred is poured on the glass plate of cleaning, according to different width and thickness need
Will, the paper slip of different-thickness is fabricated to, outsourcing adhesive tape, sets horizontal width, fixes on a glass, makes low-cost die
Type, then casting are placed after obtaining the homogeneous liquid layer of thickness until occurring without bubble.
Embodiment seven：Present embodiment is that the preparation PVdF/PVA/MMT described in embodiment one is consolidated
The further explanation of the method for body polymer electrolyte film, is put into vacuum drying chamber by glass plate in the step 7 and is dried
Dry-cure, 120 DEG C of heating-up temperature, takes out after time 60min clock stand-by.Before vacuum drying, five oxidations are placed in drying box
Two phosphorus, to absorb the solvent steamed without damaging drying box.Film is washed into the identical disk of size with the sheet-punching machine of 14mm,
In case used during packed battery.
Claims (1)
1. a kind of method for preparing PVdF/PVA/MMT solid polymer electrolyte films, it includes the following steps：
Step 1：By stand-by PVdF, PVA is positioned over drying box drying process；
Step 2：By 0.5gPVdF be dissolved in 2-3mlDMF solvents 15 it is small when, 2wt%-6wt%MMT is dissolved in 1-2mlTHF solvents
15 it is small when, the two mixing is further continued for stirring 15 it is small when ensure Polymer Solution it is uniform and stable；
Step 3：The solution being stirred is ultrasonically treated 5-10 minutes；
Step 4：First by 0.1gPVA be dissolved in 1-2mlDMF solvents 2 it is small when, the solution with being mixed with PVdF and MMT continues to mix, and adds
Enter appropriate lithium salts and continue stirring 6 it is small when until solution it is uniform and stable；
Step 5：Repeat step three；
Step 6：According to different width and thickness needs, the paper slip of different-thickness is made, outsourcing adhesive tape, sets water
Flat width, is fixed on cleaned glass plate, makes simple model, then the Polymer Solution being stirred is poured over to the glass of cleaning
In glass plate, casting is placed after obtaining the homogeneous liquid layer of thickness until occurring without bubble；
Step 7：Glass plate is put into vacuum drying chamber and carries out drying and processing, 120 DEG C of heating-up temperature, takes out after time 60min clock
It is stand-by；Before drying and processing, phosphorus pentoxide is placed in drying box, to absorb the solvent steamed without damaging drying box；
Film is washed into the identical disk of size with the sheet-punching machine of 14mm after drying and processing, in case being used during packed battery.
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| CN109888382B (en) * | 2019-04-15 | 2022-05-03 | 哈尔滨理工大学 | Preparation method of clay-reinforced polymer solid electrolyte film |
| CN110048159A (en) * | 2019-04-27 | 2019-07-23 | 枣庄市产品质量监督检验所 | A kind of sulfur-containing polymer lithium cell electrolyte preparation method |
| CN113851704B (en) * | 2021-09-24 | 2023-12-15 | 中化学南方建设投资有限公司 | Preparation method of polymer electrolyte membrane |
| CN114188667A (en) * | 2021-11-18 | 2022-03-15 | 哈尔滨工业大学 | Composite diaphragm of rechargeable lithium ion battery and preparation method and application thereof |
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| CN103199301A (en) * | 2013-01-23 | 2013-07-10 | 浙江地坤键新能源科技有限公司 | Composite gel polymer electrolyte based on solid polymer electrolyte, and preparation method and application thereof |
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