CN104600357B - Polymer composites solid electrolyte and preparation method thereof - Google Patents
Polymer composites solid electrolyte and preparation method thereof Download PDFInfo
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- CN104600357B CN104600357B CN201410745343.0A CN201410745343A CN104600357B CN 104600357 B CN104600357 B CN 104600357B CN 201410745343 A CN201410745343 A CN 201410745343A CN 104600357 B CN104600357 B CN 104600357B
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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
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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
- 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
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The invention discloses a kind of polymer composites solid electrolyte and preparation method thereof, waterborne polymeric, and the method that solid electrolyte is prepared with multi isocyanate crosslinking are filled by inorganic nano-particle and lithium salts, belong to technical field of lithium ion.It is characterized in, based on aqueous solution casting method, electrolyte being obtained using 60%~80% waterborne polymeric, 10%~40% lithium salts, 2.0%~8.0% inorganic nano-filler and 2.0%~8.0% polyisocyanate crosslinker.The characteristics of having ionic conductivity high, good mechanical performance and short slack time using the made polymer composites of this method, its moulding process is simple and meets environment protection requirement.
Description
Technical field
The present invention relates to a kind of electrolyte and preparation method thereof, particularly a kind of composite solid electrolyte and its preparation
Method, is applied to technical field of lithium ion secondary.
Background technology
Lithium ion battery with high voltage, high-energy-density, has extended cycle life and nothing as a kind of green high-efficient new energy
The advantages of memory effect, it is widely used on the mancarried electronic aids such as mobile communication, notebook computer and microcam, and
Be also show well in fields such as electric powered motor power supply, intelligent grid energy-storage system, MEMS and Aero-Space
Application prospect.Electrolyte is one of core parts of lithium battery, conduction electric current is not only played between positive and negative electrode and is transported
The effect of ion, and the working mechanism of battery is largely determined, it is influence battery specific energy, security, circulation
The key factor of performance and high rate performance etc..
The electrolyte of lithium ion battery can be divided into liquid electrolyte, solid electrolyte and solid-liquid composite electrolyte three major types.
Although liquid electrolyte or the compound gel polymer electrolyte of solid-liquid are commercial on a large scale, the carbonic ester containing easy to leak
Class organic solvent so that battery has the huge potential safety hazard such as catch fire, explode, and is particularly particularly acute under abuse state, such as
In thermal shock, mistake discharge charge and short circuit, security incident may occur when battery is used.Because being free of any organic solvent, and have
The remarkable advantages, high-performance polymerization such as reactivity low, cycle performance is good, the easy to process and encapsulation of safety and electrode material
Thing composite solid electrolyte is the indispensable part of lithium battery of new generation.
Full solid state polymer electrolyte battery has high, easy, the safe and reliable and flexible design of manufacture of energy density etc. excellent
Point, the Developing mainstream as following electrochmical power source.But, existing polyethylene glycol oxide (PEO), polyacrylonitrile (PAN) and poly- first
The ionic conductivity and mechanical property of base methyl acrylate (PMMA) base solid polymer electrolyte are relatively low, and in forming process
Substantial amounts of organic solvent need to be used, as the principal element for restricting its development.
The content of the invention
In order to overcome the shortcomings of that prior art is present, the present invention provide a kind of polymer composites solid electrolyte and its
Preparation method, made composite not only has the advantages that ionic conductivity is high, good mechanical performance, and slack time
Short, its moulding process is simple and meets environment protection requirement.
Purpose is created to reach foregoing invention, the present invention uses following technical proposals：
A kind of polymer composites solid electrolyte, by waterborne polymeric, lithium salts, inorganic nano-particle and polyisocyanic acid
The all material components of ester are combined, and each material component matches as follows according to component dry mass percentage：
Waterborne polymeric 40.0-80.0 wt%
Lithium salts 15.0-40.0 wt%
Inorganic nano-filler 2.0-10.0 wt%
Polyisocyanates 3.0-10.0 wt%
Above-mentioned waterborne polymeric is preferably using in polyvinyl alcohol, polyvinyl acetate-ethene latex powder and carboxymethylcellulose calcium
Any one or any several mixture.
Above-mentioned lithium salts is preferably using any one in lithium perchlorate, lithium carbonate, lithium sulfate and lithium nitrate or any several
Mixture.
Above-mentioned inorganic nano-filler is preferably less than in 100 nanometers of silica, titanium dioxide and calcium carbonate using particle diameter
Any one nanoparticulate fillers or any several nanoparticulate fillers mixture.
Above-mentioned polyisocyanates is preferably not less than 2.85 using water dispersible polymeric multi isocyanate and average functionality
Any one in high functionality polymeric multi isocyanate or the mixture both it.
A kind of preparation method of Inventive polymers composite solid electrolyte, based on aqueous solution casting method, each raw material
Component according to component dry mass percentage match, using the waterborne polymeric of 60~80wt%, the lithium salts of 10~40wt%, 2.0~
The polyisocyanate crosslinker of the inorganic nano-filler of 8.0 wt% and 2.0~8.0 wt% prepares polymer composite as raw material
Material solid electrolyte, concretely comprises the following steps：
A. by waterborne polymeric and deionized water according to 1:10 quality proportioning is added in reactor, is to slowly warm up to 60-95
DEG C, mechanical agitation 1-2 hours so that it becomes the aqueous polymer solution being evenly distributed；
B. it is cooled to 50 DEG C, and to adding lithium salts, further machinery to stir in the aqueous polymer solution prepared in step a
Mix 2-3 hours, lithium salts is dissolved completely in aqueous polymer solution；
C. continue to be cooled to 30-40 DEG C, by aqueous point of the nano-particle that the solid content containing inorganic nano-filler is 20 wt %
Dispersion liquid is slowly added into the aqueous polymer solution of the dissolving lithium salts for preparing in stepb, common with churned mechanically in ultrasonic wave
Under same-action, mix 2-3 hours, inorganic nano-filler is scattered in mixed liquor；
D. to polymeric isocyanate is added dropwise in the mixed liquor prepared in the step c, and stir 15-30 minutes；
E. the mixed liquor prepared in step d is poured into polytetrafluorethylecoatings coatings mould, 48 is stood at room temperature small
Shi Hou, in being dried 72 hours at 30-40 DEG C in vacuum drying chamber, obtains dielectric film；
F. will in step e dried dielectric film, hot setting is eliminated after at least 24 hours under the conditions of 140 DEG C
The isocyanate groups remained in dielectric film, final prepared thickness is 20-60 μm of solid electrolyte film.
The present invention compared with prior art, substantive distinguishing features and remarkable advantage is obviously protruded with following：
1. it is not simple blending between lithium salts and waterborne polymeric segment in the solid electrolyte that prepared by the present invention, and
It is to form effective ligand, the migration of lithium ion, lithium salts influence is realized by the complexing-solution complexation process for being coordinated this
The regularity of polymer molecule segment, reduces polymer dielectric crystallinity and fusing point, so that molecule segment warm-up movement
Ability strengthens；- the NCO of polymeric isocyanate can chemically react with the hydroxyl in waterborne polymeric, make inside electrolyte
Spatial network is formed, being heated by " post processing " then makes the NCO group of remnants further be crosslinked, change the regular of segment arrangement
Property, further improve the locomitivity of segment；And nano inorganic particle can reduce the crystallizing power of macromolecular material, increase nothing
Setting zone content；
2. polymer composites solid electrolyte has ionic conductivity high and mechanical property obtained in the inventive method
Excellent the characteristics of；
3. the method that the present invention is used is compared with existing solid polyelectrolyte preparation method, not only the property of product
Can be more superior, it is to avoid the release of organic solvent, and can significantly reduce production cost.
Specific embodiment
Details are as follows for the preferred embodiments of the present invention：
Embodiment one：
In the present embodiment, the preparation method of polymer composites solid electrolyte, based on aqueous solution casting method, step
It is as follows：
A. 600 parts of cold water are injected in reactor, starts mixer, add 60 parts of polyvinyl alcohol of alcoholysis degree 88%, delayed
Slow to be warming up to 90 DEG C, mechanical mixture obtains homogeneous solution in 2 hours；
B. 50 DEG C are cooled to, 30 parts of lithium perchlorates are added, are stirred 2.5 hours, it is dissolved completely in polyvinyl alcohol water-soluble
In liquid；
C. continue to be cooled to 40 DEG C, by 25 parts of aqueous liquid dispersions of Nano particles of silicon dioxide（Solid content 20%）Slowly plus
Enter, under ultrasonic wave with churned mechanically collective effect, mix 3 hours；
D. 5 parts of water dispersible polymeric isocyanates are added dropwise, and stir 15-30 minutes；
E. above-mentioned solution is poured into after being stored at room temperature 48 hours in polytetrafluorethylecoatings coatings mould, in vacuum drying chamber
Dried 72 hours at 40 DEG C；
F. dried dielectric film is solidified 24 hours in 140 DEG C ,-the NCO that elimination is wherein remained, it is 25 to obtain thickness
μm solid electrolyte film.
Embodiment two：
The present embodiment is essentially identical with embodiment one, is particular in that：
In the present embodiment, the preparation method of polymer composites solid electrolyte, step is as follows：
A. 600 parts of cold water are injected in reactor, starts mixer, add 55 parts of polyvinyl acetate-ethene breast（VAE）
Rubber powder, is to slowly warm up to 60 DEG C, and mechanical mixture obtains homogeneous solution in 2 hours；
B. 50 DEG C are cooled to, 35 parts of lithium carbonates are added, are stirred 3 hours, it is dissolved completely in VAE solution；
C. continue to be cooled to 30-40 DEG C, by 30 parts of nano-calcium carbonate aqueous liquid dispersions（Solid content 20%）It is slowly added into,
Under ultrasonic wave and churned mechanically collective effect, mix 2.5 hours；
D. 4 parts of water dispersible polymeric multi isocyanates are added dropwise, and stir 15-30 minutes；
E. this step is identical with embodiment one；
F. dried dielectric film is solidified 24 hours in 140 DEG C ,-the NCO that elimination is wherein remained, it is 35 to obtain thickness
μm solid electrolyte film.
Embodiment three：
The present embodiment is substantially the same as in the previous example, and is particular in that：
In the present embodiment, the preparation method of polymer composites solid electrolyte, step is as follows：
A. 600 parts of cold water are injected in reactor, starts mixer, add 50 parts of polyvinyl alcohol and 10 of alcoholysis degree 99%
Part carboxymethylcellulose calcium, is to slowly warm up to 95 DEG C, and mechanical mixture obtains homogeneous solution in 2 hours；
B. 50 DEG C are cooled to, 30 parts of lithium sulfates are added, are stirred 2.5 hours, it is dissolved completely in polyvinyl alcohol and carboxylic first
In the mixed aqueous solution of base cellulose；
C. continue to be cooled to 30-40 DEG C, by 20 parts of nano titanium dioxide water-dispersion liquids（Solid content 20%）It is slowly added into,
Under ultrasonic wave and churned mechanically collective effect, mix 3 hours；
D. 6 parts of high functionality polymeric multi isocyanates are added dropwise, and stir 15-30 minutes；
E. this step is identical with embodiment one；
F. dried dielectric film is solidified 24 hours in 140 DEG C ,-the NCO that elimination is wherein remained, it is 30 to obtain thickness
μm solid electrolyte film.
Material property analysis test：
Main performance according to the made solid electrolyte of one ~ embodiment of embodiment three detected, is compared as follows table 1.
The main physico-mechanical performance of the embodiment of the present invention solid electrolyte of table 1.
From table 1, polymer composites solid electrolyte of the invention have good normal temperature ionic conductivity and
Mechanical property, its slack time of what is more important is smaller, it can be ensured that service ability steady in a long-term.The present invention is received using inorganic
Rice corpuscles, lithium salts, modified polyisocyanate waterborne polymeric prepare total solids electrolyte, can be widely applied to lithium ion secondary electricity
Pond industrial circle.
The embodiment of the present invention is illustrated above, but the invention is not restricted to above-described embodiment, can also be according to this hair
The purpose of bright innovation and creation makes various changes, and that is done under the Spirit Essence and principle of all foundation technical solution of the present invention changes
Become, modify, substitute, combine, simplify, equivalent substitute mode is should be, as long as meeting goal of the invention of the invention, as long as not carrying on the back
Know-why and inventive concept from Inventive polymers composite solid electrolyte and preparation method thereof, belong to the present invention
Protection domain.
Claims (2)
1. a kind of polymer composites solid electrolyte, by waterborne polymeric, lithium salts, inorganic nano-particle and polyisocyanates
All material components are combined by a certain percentage, it is characterised in that each material component is according to component dry mass percentage with such as
Under：
Waterborne polymeric 40.0-80.0
Lithium salts 15.0-40.0
Inorganic nano-particle 2.0-10.0
Polyisocyanates 3.0-10.0
Above-mentioned each material component constitutes 100% ingredients mixture；
The specific raw material for using is as follows in above-mentioned each material component：
Waterborne polymeric is the mixing of any one or two kinds in polyvinyl acetate-ethene latex powder and carboxymethylcellulose calcium
Thing；
Lithium salts is any one or any several mixture in lithium perchlorate, lithium carbonate, lithium sulfate and lithium nitrate；
Inorganic nano-filler is any one nanometer in silica of the particle diameter less than 100 nanometers, titanium dioxide and calcium carbonate
The mixture of particle filler or any several nanoparticulate fillers；
Polyisocyanates is that the high functionality polymerization of water dispersible polymeric multi isocyanate and average functionality not less than 2.85 is more
Any one in isocyanates or the mixture both it.
2. a kind of preparation method of polymer composites solid electrolyte according to claim 1, it is characterised in that：Should
Method is based on aqueous solution casting method, and each material component is matched according to component dry mass percentage, uses the aqueous poly- of 60~80wt%
The multi isocyanate crosslinking of compound, the lithium salts of 10~40wt%, the inorganic nano-filler of 2.0~8.0 wt% and 2.0~8.0 wt%
Agent prepares polymer composites solid electrolyte as raw material, and waterborne polymeric is polyvinyl acetate-ethene latex powder and carboxylic
The mixture of any one or two kinds in methylcellulose, concretely comprises the following steps:
A. by waterborne polymeric and deionized water according to 1:10 quality proportioning is added in reactor, is to slowly warm up to 60-95 DEG C,
Mechanical agitation 1-2 hours so that it becomes the aqueous polymer solution being evenly distributed；
B. 50 DEG C are cooled to, and to lithium salts is added in the aqueous polymer solution prepared in the step a, it is further mechanical
Stirring 2-3 hours, makes lithium salts be dissolved completely in aqueous polymer solution；
C. continue to be cooled to 30-40 DEG C, by the nano-particle aqueous dispersion that the solid content containing inorganic nano-filler is 20 wt %
Liquid be slowly added into the step b prepare dissolving lithium salts aqueous polymer solution in, ultrasonic wave with it is churned mechanically
Under collective effect, mix 2-3 hours, inorganic nano-filler is scattered in mixed liquor；
D. to polymeric isocyanate is added dropwise in the mixed liquor prepared in the step c, and stir 15-30 minutes；
E. the mixed liquor prepared in the step d is poured into polytetrafluorethylecoatings coatings mould, 48 is stood at room temperature small
Shi Hou, in being dried 72 hours at 30-40 DEG C in vacuum drying chamber, obtains dielectric film,
F. will in the step e dried dielectric film, hot setting is eliminated after at least 24 hours under the conditions of 140 DEG C
The isocyanate groups remained in dielectric film, final prepared thickness is 20-60 μm of solid electrolyte film.
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| JP6977932B2 (en) | 2015-08-17 | 2021-12-08 | 地方独立行政法人大阪産業技術研究所 | Additives for all-solid-state secondary batteries, all-solid-state secondary batteries and methods for manufacturing them |
| US10497968B2 (en) * | 2016-01-04 | 2019-12-03 | Global Graphene Group, Inc. | Solid state electrolyte for lithium secondary battery |
| CN105860114B (en) * | 2016-03-21 | 2018-11-30 | 青岛科技大学 | A kind of preparation method of cellulose nano-fibrous solid electrolyte membrane |
| US10084220B2 (en) * | 2016-12-12 | 2018-09-25 | Nanotek Instruments, Inc. | Hybrid solid state electrolyte for lithium secondary battery |
| CN108469388B (en) * | 2018-02-01 | 2020-11-24 | 上海大学 | Prediction method of dynamic storage modulus of high polymer under damp and hot conditions |
| CN108520959B (en) * | 2018-03-20 | 2021-06-04 | 上海大学 | Water-based polymer-isocyanate-based electrode composite material and preparation method thereof |
| CN109004280B (en) * | 2018-07-11 | 2021-06-08 | 珠海冠宇电池股份有限公司 | Preparation method of all-solid-state polymer electrolyte and all-solid-state polymer battery |
| CN109326822B (en) * | 2018-11-05 | 2020-11-17 | 珠海冠宇电池股份有限公司 | Preparation method of all-solid fluoropolymer electrolyte membrane and lithium ion battery |
| CN111969245B (en) * | 2020-04-17 | 2022-05-10 | 中国科学院青岛生物能源与过程研究所 | High-safety solid electrolyte and preparation method and application thereof |
| CN111786017B (en) * | 2020-04-17 | 2022-06-21 | 中国科学院青岛生物能源与过程研究所 | High-cohesiveness solid electrolyte prepared by in-situ curing, preparation method and application |
| CN112234314B (en) * | 2020-09-28 | 2023-05-05 | 佛山市金辉高科光电材料股份有限公司 | Composite slurry, lithium battery separator and preparation method and application of lithium battery separator |
| CN112713301B (en) * | 2020-12-31 | 2022-06-24 | 广东微电新能源有限公司 | Energy storage device |
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| EP0850933A1 (en) * | 1996-12-30 | 1998-07-01 | Centre National De La Recherche Scientifique (Cnrs) | Salts of pentacyclic or tetrapentaline derived anions, and their uses as ionic conductive materials |
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| CN101325130A (en) * | 2008-05-22 | 2008-12-17 | 清华大学 | Poly-pyrrole minisize super capacitor based on MEMS technique and method for manufacturing the same |
| CN101515655A (en) * | 2009-03-16 | 2009-08-26 | 清华大学 | Three dimensional structure micro zinc-nickel battery applying to microsystems and preparation method thereof |
| CN103474696A (en) * | 2013-08-27 | 2013-12-25 | 中南大学 | Organic-inorganic hybrid polymeric solid electrolyte material and application thereof |
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