CN109244537A - Composite solid electrolyte, preparation method and its application - Google Patents
Composite solid electrolyte, preparation method and its application Download PDFInfo
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- CN109244537A CN109244537A CN201811118625.2A CN201811118625A CN109244537A CN 109244537 A CN109244537 A CN 109244537A CN 201811118625 A CN201811118625 A CN 201811118625A CN 109244537 A CN109244537 A CN 109244537A
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
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Abstract
The invention discloses a kind of composite solid electrolyte, preparation method and its applications, the solid state electrolysis plastidome is made of pre-prepared polymer, in-situ polymerization high molecular material and lithium salts, and wherein in-situ polymerization high molecular material by vinyl-ethers organic monomer by effect of irradiation, generated in electrode material surface in-situ polymerization.The present invention can make the conductivity at room temperature σ > 10 of solid electrolyte‑ 5S·cm‑1, corresponding solid state battery is 100 weeks or more recyclable at room temperature, and capacity retention ratio is greater than 90%.Composite solid electrolyte of the present invention does not need the means such as hot-forming using irradiance method preparation, has environmental protection, low energy consumption, advantage at low cost；Composite solid electrolyte preparation method of the present invention is simple, compatible with prior art good.Solid polyelectrolyte system of the invention is suitble to industrial application, is with a wide range of applications in power battery and energy-storage battery field.
Description
Technical field
The present invention relates to a kind of electrolyte, preparation method and its applications, more particularly to a kind of solid electrolyte, its system
Preparation Method and its application are applied to secondary lithium battery technical field of energy storage.
Background technique
Lithium ion battery has that operating voltage is high, energy density is high, have extended cycle life, memory-less effect and environmental-friendly etc.
Feature is widely used in the portable electronic devices such as mobile phone, laptop, miniature camera.With electronic vapour
The development of vehicle, large-scale energy storage device etc., there is an urgent need to higher power density, higher energy density, more long circulation life, more preferable peaces
The lithium ion battery of full property.Traditional liquid electrolyte security risk poor there are inflammable, thermal stability, therefore there is an urgent need to send out
Open up all-solid-state battery.Solid electrolyte is non-ignitable and can inhibit Li dendrite, makes it possible the use of lithium metal.But solid state electrolysis
The interface impedance of matter and positive electrode is big, becomes the bottleneck for restricting all-solid-state battery development, and solid electrolyte common at present
Room-temperature conductivity about 10-6S·cm-1, far below the conductivity of liquid electrolyte.Therefore solid state battery interface impedance reduction and
The raising of electrolyte ion conductance, it will greatly accelerate the research and application of all-solid-state battery.But the room of current solid electrolyte
Warm ionic conductivity is to be improved, and the comprehensive performance of solid electrolyte is also undesirable, higher cost.
Summary of the invention
In order to solve prior art problem, it is an object of the present invention to overcome the deficiencies of the prior art, and to provide one kind
Composite solid electrolyte, preparation method and its application, the mixing using pre-polymerized materials and in-situ polymerization high molecular material make
With, the lithium ion conductance of electrolyte can be effectively improved, be effectively improved solid electrolyte and anode interfacial contact, reduce interface resistance
It is anti-, improve battery performance.The present invention carries out in-situ polymerization using irradiation, can be effectively controlled polymer polymerizing degree, improves interface
Contact, does not need the means such as hot-forming, has environmental protection, low energy consumption, advantage at low cost.
In order to achieve the above objectives, the present invention adopts the following technical scheme:
A kind of composite solid electrolyte is mainly grouped by pre-prepared polymer, in-situ polymerization high molecular material and lithium salts group
At according to the calculating of constituent mass degree, the constituent content of pre-prepared high molecular polymer is whole solid electrolyte
10~90wt%, the constituent content of lithium salts are 1~50wt% of whole solid electrolyte, and wherein in-situ polymerization high molecular material
It by one or more vinyl-ethers organic monomer by effect of irradiation, is generated in electrode material surface in-situ polymerization, and in spoke
So that pre-prepared polymer, in-situ polymerization high molecular material and lithium salts is carried out solidification combination according under the conditions of, forms composite solid electrolysis
Matter.
As currently preferred technical solution, above-mentioned vinyl-ethers organic monomer chemical formula are as follows:
Wherein R1For both arms or multi-arm fat alkane/ether functional group, R2For the bridge linkage group containing carbon atom 1~10.
The technical solution further preferred as the present invention, above-mentioned vinyl-ethers organic monomer are with following chemistry
At least one of monomer of formula:
Monomer 1:
Monomer 2:
Monomer 3:
Above-mentioned pre-prepared high molecular polymer preferably uses the group of one or more of following organic matter and its derivative
It closes: polyethylene oxide (PEO), polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), Kynoar (PVDF), polycyclic
Ethylene Oxide (PPO), Vingon (PVDC), poly- ethylene carbonate (PEC), polytrimethylene carbonate (PTMC), poly- carbonic acid
Acrylic ester (PPC).
Above-mentioned lithium salts preferably uses LiClO4、LiPF6、LiBF4、LiAsF6, LiFSI, LiTFSI and other are fluorine-containing/nitrogen yin
At least one of ionic lithium salts lithium salts.
Above-mentioned irradiation used preferably uses the wavelength of ultraviolet light for 300~400nm.
A kind of preparation method of composite solid electrolyte of the present invention, includes the following steps:
A. using one or more vinyl-ethers organic monomer, initiator, pre-prepared high molecular polymer, lithium salts
Mixture is calculated as raw material according to constituent mass degree, and the constituent content of pre-prepared high molecular polymer is raw material
10~80wt% of total amount, the constituent content of lithium salts are 1~50wt% of raw material total amount, and raw material is stirred evenly in a solvent,
Obtain mixed slurry；It is preferred that using the quality of vinyl-ethers organic monomer, initiator, pre-prepared high molecular polymer, lithium salts
Than for 3:0.01:(1~1.5): 2；Above-mentioned solvent preferably uses acetonitrile；
B. the mixed slurry obtained in the step a is coated in positive electrode surface, forms slurry film；
C. it is irradiated under the positive electrode of the coating slurry film in the step b being placed in ultraviolet lamp, until slurry film is solid
It is melted into solid film, and by heating method, vacuum mode or using heating and the vacuum combined mode of action, is further removed molten
Agent, thus the composite solid electrolyte that preparation is combined closely with positive electrode surface.
A kind of application of composite solid electrolyte of the present invention combines composite solid electrolyte film, group on positive electrode surface
Fill secondary lithium battery.
The present invention compared with prior art, has following obvious prominent substantive distinguishing features and remarkable advantage:
1. composite polymeric solid electrolyte of the present invention and preparation method thereof can generate admittedly on anode surface by irradiation
State dielectric film is effectively improved the interfacial contact of solid electrolyte and anode, reduces interface impedance, improves battery performance；
2. composite solid electrolyte of the present invention is prepared using irradiance method, the means such as hot-forming are not needed, there is environmental protection,
Low energy consumption, advantage at low cost, composite solid electrolyte preparation method is simple, compatible with prior art good；
3. solid polyelectrolyte system of the invention is suitble to industrial application, have in power battery and energy-storage battery field
Have wide practical use.
Specific embodiment
Above scheme is described further below in conjunction with specific implementation example, the preferred embodiment of the present invention is described in detail such as
Under:
Embodiment one
In the present embodiment, a kind of preparation method of composite solid electrolyte of the present invention, includes the following steps:
A. the mixture conduct of vinyl-ethers organic monomer, initiator, pre-prepared high molecular polymer, lithium salts is used
Raw material, medium vinyl-ethers organic monomer use monomer 1:
Pre-prepared high molecular polymer uses PEO；Lithium salts uses
LiTFSI；It is 3:0.01 by the mass ratio of vinyl-ethers organic monomer, initiator, pre-prepared high molecular polymer, lithium salts:
Each raw material of 1:2 stirs evenly in acetonitrile solvent, is dissolved in acetonitrile, obtains mixed slurry；
B. the mixed slurry obtained in the step a is coated in LiFePO4Pole piece forms slurry film；
C. it is irradiated under the positive electrode of the coating slurry film in the step b being placed in ultraviolet lamp, irradiation is using purple
The wavelength of outside line is 365nm, until slurry film is solidified into solid film, and by using drying heating and the vacuum combined mode of action,
Solvent is further removed, thus the composite solid electrolyte that preparation is combined closely with positive electrode surface.
By LiFePO manufactured in the present embodiment4Pole piece positive electrode surface combines composite solid electrolyte film as component,
It is that battery testing is assembled to electrode with lithium piece, test was met referring to table 1.The present embodiment prepares the room-temperature ion electricity of solid electrolyte
Conductance σ > 10-5S·cm-1.The present embodiment carries out in-situ polymerization by irradiation, can effectively control polymer polymerizing degree, change
Kind interfacial contact；Using being used in mixed way for pre-polymerized materials and in-situ polymerization high molecular material, electrolyte can effectively improve
Lithium ion conductance.Low, the electrolyte ion conductance height, it will greatly accelerate complete of solid state battery interface impedance manufactured in the present embodiment
The research and application of solid state battery.
Embodiment two
The present embodiment is basically the same as the first embodiment, and is particular in that:
In the present embodiment, a kind of preparation method of composite solid electrolyte of the present invention, includes the following steps:
A. the mixture conduct of vinyl-ethers organic monomer, initiator, pre-prepared high molecular polymer, lithium salts is used
Raw material, medium vinyl-ethers organic monomer use monomer 1:
Pre-prepared high molecular polymer uses PEO；Lithium salts uses
LiTFSI；It is 3:0.01 by the mass ratio of vinyl-ethers organic monomer, initiator, pre-prepared high molecular polymer, lithium salts:
Each raw material of 1.5:2 stirs evenly in acetonitrile solvent, is dissolved in acetonitrile, obtains mixed slurry；
B. the mixed slurry obtained in the step a is coated in LiFePO4Pole piece forms slurry film；
C. it is irradiated under the positive electrode of the coating slurry film in the step b being placed in ultraviolet lamp, irradiation is using purple
The wavelength of outside line is 365nm, until slurry film is solidified into solid film, and by using drying heating and the vacuum combined mode of action,
Solvent is further removed, thus the composite solid electrolyte that preparation is combined closely with positive electrode surface.
By LiFePO manufactured in the present embodiment4Pole piece positive electrode surface combines composite solid electrolyte film as component,
It is that battery testing is assembled to electrode with lithium piece, test was met referring to table 1.The present embodiment prepares the room-temperature ion electricity of solid electrolyte
Conductance σ > 10-5S·cm-1.The present embodiment carries out in-situ polymerization by irradiation, can effectively control polymer polymerizing degree, change
Kind interfacial contact；Using being used in mixed way for pre-polymerized materials and in-situ polymerization high molecular material, electrolyte can effectively improve
Lithium ion conductance.Low, the electrolyte ion conductance height, it will greatly accelerate complete of solid state battery interface impedance manufactured in the present embodiment
The research and application of solid state battery.
Embodiment three
The present embodiment is substantially the same as in the previous example, and is particular in that:
In the present embodiment, a kind of preparation method of composite solid electrolyte of the present invention, includes the following steps:
A. the mixture conduct of vinyl-ethers organic monomer, initiator, pre-prepared high molecular polymer, lithium salts is used
Raw material, medium vinyl-ethers organic monomer use monomer 2:
Pre-prepared high molecular polymer uses PEO；Lithium salts uses LiTFSI；
It is each of 3:0.01:1:2 by the mass ratio of vinyl-ethers organic monomer, initiator, pre-prepared high molecular polymer, lithium salts
Raw material stirs evenly in acetonitrile solvent, is dissolved in acetonitrile, obtains mixed slurry；
B. the mixed slurry obtained in the step a is coated in LiFePO4Pole piece forms slurry film；
C. it is irradiated under the positive electrode of the coating slurry film in the step b being placed in ultraviolet lamp, irradiation is using purple
The wavelength of outside line is 365nm, until slurry film is solidified into solid film, and by using drying heating and the vacuum combined mode of action,
Solvent is further removed, thus the composite solid electrolyte that preparation is combined closely with positive electrode surface.
By LiFePO manufactured in the present embodiment4Pole piece positive electrode surface combines composite solid electrolyte film as component,
It is that battery testing is assembled to electrode with lithium piece, test was met referring to table 1.The present embodiment prepares the room-temperature ion electricity of solid electrolyte
Conductance σ > 10-5S·cm-1.The present embodiment carries out in-situ polymerization by irradiation, can effectively control polymer polymerizing degree, change
Kind interfacial contact；Using being used in mixed way for pre-polymerized materials and in-situ polymerization high molecular material, electrolyte can effectively improve
Lithium ion conductance.Low, the electrolyte ion conductance height, it will greatly accelerate complete of solid state battery interface impedance manufactured in the present embodiment
The research and application of solid state battery.
Example IV
The present embodiment is substantially the same as in the previous example, and is particular in that:
In the present embodiment, a kind of preparation method of composite solid electrolyte of the present invention, includes the following steps:
A. the mixture conduct of vinyl-ethers organic monomer, initiator, pre-prepared high molecular polymer, lithium salts is used
Raw material, medium vinyl-ethers organic monomer use monomer 2:
Pre-prepared high molecular polymer uses the mixture of PEO and PAN,
The mass ratio of middle PEO and PAN is 1；1；Lithium salts uses LiTFSI；By vinyl-ethers organic monomer, initiator, pre-prepared height
Molecularly Imprinted Polymer, each raw material that the mass ratio of lithium salts is 3:0.01:1:2 stir evenly in acetonitrile solvent, are dissolved in acetonitrile, obtain
Mixed slurry；
B. the mixed slurry obtained in the step a is coated in LiFePO4Pole piece forms slurry film；
C. it is irradiated under the positive electrode of the coating slurry film in the step b being placed in ultraviolet lamp, irradiation is using purple
The wavelength of outside line is 365nm, until slurry film is solidified into solid film, and by using drying heating and the vacuum combined mode of action,
Solvent is further removed, thus the composite solid electrolyte that preparation is combined closely with positive electrode surface.
By LiFePO manufactured in the present embodiment4Pole piece positive electrode surface combines composite solid electrolyte film as component,
It is that battery testing is assembled to electrode with lithium piece, test was met referring to table 1.The present embodiment prepares the room-temperature ion electricity of solid electrolyte
Conductance σ > 10-5S·cm-1.The present embodiment carries out in-situ polymerization by irradiation, can effectively control polymer polymerizing degree, change
Kind interfacial contact；Using being used in mixed way for pre-polymerized materials and in-situ polymerization high molecular material, electrolyte can effectively improve
Lithium ion conductance.Low, the electrolyte ion conductance height, it will greatly accelerate complete of solid state battery interface impedance manufactured in the present embodiment
The research and application of solid state battery.
Embodiment five
The present embodiment is substantially the same as in the previous example, and is particular in that:
In the present embodiment, a kind of preparation method of composite solid electrolyte of the present invention, includes the following steps:
A. the mixture conduct of vinyl-ethers organic monomer, initiator, pre-prepared high molecular polymer, lithium salts is used
Raw material, medium vinyl-ethers organic monomer use monomer 3:
Pre-prepared high molecular polymer uses PEO；Lithium salts uses LiTFSI；It will
Vinyl-ethers organic monomer, initiator, pre-prepared high molecular polymer, lithium salts mass ratio be 3:0.01:1:2 each original
Material stirs evenly in acetonitrile solvent, is dissolved in acetonitrile, obtains mixed slurry；
B. the mixed slurry obtained in the step a is coated in LiFePO4Pole piece forms slurry film；
C. it is irradiated under the positive electrode of the coating slurry film in the step b being placed in ultraviolet lamp, irradiation is using purple
The wavelength of outside line is 365nm, until slurry film is solidified into solid film, and by using drying heating and the vacuum combined mode of action,
Solvent is further removed, thus the composite solid electrolyte that preparation is combined closely with positive electrode surface.
By LiFePO manufactured in the present embodiment4Pole piece positive electrode surface combines composite solid electrolyte film as component,
It is that battery testing is assembled to electrode with lithium piece, test was met referring to table 1.The present embodiment prepares the room-temperature ion electricity of solid electrolyte
Conductance σ > 10-5S·cm-1.The present embodiment carries out in-situ polymerization by irradiation, can effectively control polymer polymerizing degree, change
Kind interfacial contact；Using being used in mixed way for pre-polymerized materials and in-situ polymerization high molecular material, electrolyte can effectively improve
Lithium ion conductance.Low, the electrolyte ion conductance height, it will greatly accelerate complete of solid state battery interface impedance manufactured in the present embodiment
The research and application of solid state battery.
Embodiment six
The present embodiment is substantially the same as in the previous example, and is particular in that:
In the present embodiment, a kind of preparation method of composite solid electrolyte of the present invention, includes the following steps:
A. the mixture conduct of vinyl-ethers organic monomer, initiator, pre-prepared high molecular polymer, lithium salts is used
Raw material, is 100% calculating according to vinyl-ethers organic monomer gross mass, and medium vinyl-ethers organic monomer uses
The monomer 1 of 60wt% and the monomer 3 of 40wt% form；Pre-prepared high molecular polymer uses PEO；Lithium salts uses LiTFSI；It will
Vinyl-ethers organic monomer, initiator, pre-prepared high molecular polymer, lithium salts mass ratio be 3:0.01:1.5:2 it is each
Raw material stirs evenly in acetonitrile solvent, is dissolved in acetonitrile, obtains mixed slurry；
B. the mixed slurry obtained in the step a is coated in LiFePO4Pole piece forms slurry film；
C. it is irradiated under the positive electrode of the coating slurry film in the step b being placed in ultraviolet lamp, irradiation is using purple
The wavelength of outside line is 365nm, until slurry film is solidified into solid film, and by using drying heating and the vacuum combined mode of action,
Solvent is further removed, thus the composite solid electrolyte that preparation is combined closely with positive electrode surface.
By LiFePO manufactured in the present embodiment4Pole piece positive electrode surface combines composite solid electrolyte film as component,
It is that battery testing is assembled to electrode with lithium piece, test was met referring to table 1.The present embodiment prepares the room-temperature ion electricity of solid electrolyte
Conductance σ > 10-5S·cm-1.The present embodiment carries out in-situ polymerization by irradiation, can effectively control polymer polymerizing degree, change
Kind interfacial contact；Using being used in mixed way for pre-polymerized materials and in-situ polymerization high molecular material, electrolyte can effectively improve
Lithium ion conductance.Low, the electrolyte ion conductance height, it will greatly accelerate complete of solid state battery interface impedance manufactured in the present embodiment
The research and application of solid state battery.
Experimental test and analysis:
To LiFePO prepared in the above embodiments4Pole piece positive electrode surface combines composite solid electrolyte film as group
Part is to assemble battery to electrode with lithium piece, and at room temperature, 0.01C circulation is surveyed within the scope of 2.5-3.7V vs and Li+/Li
It is as follows to try capacity result (mAh/g):
Table 1. assembles the loop test result of lithium battery using the composite solid electrolyte film of various embodiments of the present invention preparation
The above embodiment of the present invention composite solid electrolyte and preparation method thereof, the solid state electrolysis plastidome is by pre-prepared poly-
Close object, in-situ polymerization high molecular material and lithium salts are constituted, and wherein in-situ polymerization high molecular material by the organic list of vinyl-ethers
Body is generated by effect of irradiation in electrode material surface in-situ polymerization.The above embodiment of the present invention makes the room temperature of solid electrolyte
Ionic conductivity σ > 10-5S·cm-1, corresponding solid state battery is 100 weeks or more recyclable at room temperature, and capacity retention ratio is big
In 90%.
The above embodiment of the present invention composite polymeric solid electrolyte and preparation method thereof, can be on anode surface by spoke
According to solid electrolyte membrane is generated, it is effectively improved the interfacial contact of solid electrolyte and anode, reduces interface impedance, is improved cell performance
Energy.The above embodiment of the present invention composite solid electrolyte is prepared using irradiance method, does not need the means such as hot-forming, has ring
It protects, low energy consumption, advantage at low cost.The above embodiment of the present invention composite solid electrolyte preparation method is simple, with prior art
It is compatible good.The solid polyelectrolyte system of the above embodiment of the present invention preparation is suitble to industrial application, in power battery and
Energy-storage battery field is with a wide range of applications.
The embodiment of the present invention is illustrated above, but the present invention is not limited to the above embodiments, it can also be according to this hair
The purpose of bright innovation and creation makes a variety of variations, and that does under the Spirit Essence and principle of all technical solutions according to the present invention changes
Become, modification, substitution, combination or simplified, should be equivalent substitute mode, as long as meeting goal of the invention of the invention, as long as not
Away from composite solid electrolyte of the present invention, preparation method and its technical principle of application and inventive concept, the present invention is belonged to
Protection scope.
Claims (10)
1. a kind of composite solid electrolyte, it is characterised in that: mainly by pre-prepared polymer, in-situ polymerization high molecular material and lithium
Salt group is grouped as, and is calculated according to constituent mass degree, and the constituent content of pre-prepared high molecular polymer is whole solid-state
10~90wt% of electrolyte, the constituent content of lithium salts is 1~50wt% of whole solid electrolyte, and wherein in-situ polymerization is high
Molecular material passes through effect of irradiation by one or more vinyl-ethers organic monomer, raw in electrode material surface in-situ polymerization
At, and so that pre-prepared polymer, in-situ polymerization high molecular material and lithium salts is carried out solidification combination under radiation parameter, it is formed compound
Solid electrolyte.
2. composite solid electrolyte according to claim 1, it is characterised in that: the change of the vinyl-ethers organic monomer
Formula are as follows:
Wherein R1For both arms or multi-arm fat alkane/ether functional group, R2For the bridge linkage group containing carbon atom 1~10.
3. composite solid electrolyte according to claim 2, it is characterised in that: the vinyl-ethers organic monomer is tool
There is at least one of the monomer of following chemical formula:
Monomer 1:
Monomer 2:
Monomer 3:
4. composite solid electrolyte according to claim 1, it is characterised in that: the pre-prepared high molecular polymer is using such as
The combination of one or more of lower organic matter and its derivative: polyethylene oxide (PEO), polyacrylonitrile (PAN), poly- methyl-prop
E pioic acid methyl ester (PMMA), Kynoar (PVDF), polypropylene oxide (PPO), Vingon (PVDC), poly- ethylene carbonate
(PEC), polytrimethylene carbonate (PTMC), polypropylene carbonate (PPC).
5. composite solid electrolyte according to claim 1, it is characterised in that: the lithium salts uses LiClO4、LiPF6、
LiBF4、LiAsF6, at least one of LiFSI, LiTFSI and other fluorine-containing/nitrogen anion lithium salts lithium salts.
6. composite solid electrolyte according to claim 1, it is characterised in that: it is used irradiation use the wavelength of ultraviolet light for
300~400nm.
7. a kind of preparation method of composite solid electrolyte described in claim 1, which comprises the steps of:
A. the mixing of one or more vinyl-ethers organic monomer, initiator, pre-prepared high molecular polymer, lithium salts is used
Object is calculated as raw material according to constituent mass degree, and the constituent content of pre-prepared high molecular polymer is raw material total amount
10~80wt%, the constituent content of lithium salts is 1~50wt% of raw material total amount, and raw material is stirred evenly in a solvent, is obtained
Mixed slurry；
B. the mixed slurry obtained in the step a is coated in positive electrode surface, forms slurry film；
C. it is irradiated under the positive electrode of the coating slurry film in the step b being placed in ultraviolet lamp, until slurry film is solidified into
Solid film, and by heating method, vacuum mode or using heating and the vacuum combined mode of action, solvent is further removed,
The composite solid electrolyte combined closely to preparation with positive electrode surface.
8. the preparation method of composite solid electrolyte according to claim 4, it is characterised in that: in the step a, use
Vinyl-ethers organic monomer, initiator, pre-prepared high molecular polymer, lithium salts mass ratio be 3:0.01:(1~1.5):
2。
9. the preparation method of composite solid electrolyte according to claim 4, it is characterised in that: described in the step a
Solvent uses acetonitrile.
10. a kind of application of composite solid electrolyte described in claim 1, it is characterised in that: combined on positive electrode surface multiple
Solid electrolyte membrane is closed, secondary lithium battery is assembled.
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| CN110571471A (en) * | 2019-09-27 | 2019-12-13 | 河北师范大学 | preparation method and application of solid electrolyte with post-wound rapid healing capacity |
| CN110676509A (en) * | 2019-09-02 | 2020-01-10 | 东北师范大学 | Room-temperature solid polymer electrolyte and preparation method thereof, electrode/electrolyte composite and preparation method and application thereof |
| CN110931850A (en) * | 2019-11-19 | 2020-03-27 | 上海大学 | Polysiloxane composite electrolyte, application thereof and preparation method thereof |
| CN112048036A (en) * | 2019-06-05 | 2020-12-08 | 上海大学 | Polymer electrolyte containing zwitterion group and redox group and preparation method thereof |
| CN112397769A (en) * | 2020-11-04 | 2021-02-23 | 上海大学 | Self-forming lithium iodine battery based on LiI-based small molecule composite solid electrolyte and preparation method thereof |
| CN112563563A (en) * | 2020-12-17 | 2021-03-26 | 广东微电新能源有限公司 | Composite solid electrolyte, solid battery and preparation method thereof |
| CN113451643A (en) * | 2021-06-15 | 2021-09-28 | 上海大学 | In-situ preparation method and application of amide-based composite solid electrolyte |
| CN115275337A (en) * | 2022-08-25 | 2022-11-01 | 浙江吉利控股集团有限公司 | Composite solid electrolyte membrane, preparation method thereof and lithium ion solid battery |
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