CN109088104A - Flexible solid-state battery and preparation method thereof - Google Patents
Flexible solid-state battery and preparation method thereof Download PDFInfo
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- CN109088104A CN109088104A CN201810885822.0A CN201810885822A CN109088104A CN 109088104 A CN109088104 A CN 109088104A CN 201810885822 A CN201810885822 A CN 201810885822A CN 109088104 A CN109088104 A CN 109088104A
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- flexible solid
- flexible
- electrolyte membrane
- solid electrolyte
- encapsulating film
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- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 57
- 239000012528 membrane Substances 0.000 claims abstract description 55
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000002131 composite material Substances 0.000 claims abstract description 8
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims description 107
- 239000007773 negative electrode material Substances 0.000 claims description 33
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 19
- 229910052782 aluminium Inorganic materials 0.000 claims description 18
- 238000010276 construction Methods 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 18
- 229910000733 Li alloy Inorganic materials 0.000 claims description 16
- 239000002985 plastic film Substances 0.000 claims description 16
- 229920006255 plastic film Polymers 0.000 claims description 16
- 229910052744 lithium Inorganic materials 0.000 claims description 13
- 239000001989 lithium alloy Substances 0.000 claims description 13
- 239000007774 positive electrode material Substances 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- 229910012305 LiPON Inorganic materials 0.000 claims description 7
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 6
- -1 lithium sulfur metal compound Chemical class 0.000 claims description 6
- 229910000838 Al alloy Inorganic materials 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- 229910003480 inorganic solid Inorganic materials 0.000 claims description 4
- 239000002203 sulfidic glass Substances 0.000 claims description 4
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 3
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 229910020343 SiS2 Inorganic materials 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 claims description 3
- 239000002931 mesocarbon microbead Substances 0.000 claims description 3
- 229910021382 natural graphite Inorganic materials 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 230000005611 electricity Effects 0.000 claims 4
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 5
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 5
- 150000002500 ions Chemical class 0.000 abstract description 2
- 239000011244 liquid electrolyte Substances 0.000 abstract description 2
- 229920006280 packaging film Polymers 0.000 abstract 2
- 239000012785 packaging film Substances 0.000 abstract 2
- 230000007547 defect Effects 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 239000003792 electrolyte Substances 0.000 abstract 1
- 238000009413 insulation Methods 0.000 abstract 1
- 238000004806 packaging method and process Methods 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000002002 slurry Substances 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 229910021389 graphene Inorganic materials 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000005030 aluminium foil Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000011889 copper foil Substances 0.000 description 5
- 239000007770 graphite material Substances 0.000 description 5
- 229920001021 polysulfide Polymers 0.000 description 5
- 239000005077 polysulfide Substances 0.000 description 5
- 150000008117 polysulfides Polymers 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 229910001386 lithium phosphate Inorganic materials 0.000 description 3
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000003447 ipsilateral effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000002459 sustained effect Effects 0.000 description 2
- 238000000038 ultrahigh vacuum chemical vapour deposition Methods 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 229910001080 W alloy Inorganic materials 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000012163 sequencing technique Methods 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
-
- 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
-
- 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
-
- 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
-
- 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
Abstract
The application discloses a preparation method of a flexible solid-state battery, which comprises the following steps: providing a flexible solid-state battery positive electrode; providing a flexible solid-state battery cathode; drying the positive electrode of the flexible solid-state battery and the negative electrode of the flexible solid-state battery; preparing an ultrathin flexible solid electrolyte membrane by a chemical vapor deposition method; and sequentially placing a first packaging film, the flexible solid-state battery anode, the ultrathin flexible solid-state electrolyte film, the flexible solid-state battery cathode and a second packaging film to form a first laminated structure, and completing packaging of the laminated structure. The flexible solid-state battery prepared by the method has certain tensile strength and torsional strength, has good electronic insulation and ion conductivity, can be conveniently matched with a wearable product in a composite mode, and overcomes the defect that the traditional liquid electrolyte lithium ion battery cannot meet the requirements.
Description
Technical field
This application involves technical field of solar, and in particular to flexible solid battery and preparation method thereof.
Background technique
Practical application of the battery in we live plays increasingly important role, including consumer electronics, electronic vapour
Vehicle, large, medium and small energy-storage system etc., power supply are all various types battery, wherein the lithium-ion electric to quickly grow again
Based on pond.However, commercialized lithium ion battery has not been able to satisfy the demand under product fast development gradually at present, such as require
Higher energy density, longer cycle life, and it is safer more cheap.Meanwhile as people are for personalized pursuit
Embodied with self etc. and the Intelligent mobile equipments such as intelligent, net connectionization it is universal, intelligent wearing Yue Laiyue is favored, such as intelligence
Energy bracelet, glasses, wrist-watch, shoes and hats etc., and these are intelligently dressed products and require battery to provide electric power as driving.
Battery matches with wearable product and should meet that small in size, energy is high, safety, flexibility, frivolous, continuation of the journey is long etc. wants
It asks, so traditional liquid electrolyte liquid system lithium ion battery is difficult to meet the requirements, and solid state battery or all-solid-state battery can
Perfectly to adapt to requirement of the wearable product to battery.
Solid state battery or all-solid-state battery are known as lithium by domestic and international most of scientific research institution, battery manufacturers etc.
The next-generation anchor man of ion battery, is all one after another laid out this.But solid state battery is generally acknowledged most insoluble exactly solid
The structural system of the conductivity problems at interface, especially multilayer, more targetedly researchs both at home and abroad, but make slow progress.
Summary of the invention
The preparation method and flexible solid battery of flexible solid battery provided by the present application, to solve in the prior art
The problem of conductivity problems of solid-solid interface and in the prior art battery tensile strength, torsional strength and foldability.
The application provides a kind of preparation method of flexible solid battery, comprising:
Flexible solid anode is provided；
Flexible solid battery cathode is provided；
The flexible solid anode and the flexible solid battery cathode are dried；
Ultrathin flexible solid electrolyte membrane is prepared by chemical vapour deposition technique；
First encapsulating film, the flexible solid anode, the ultrathin flexible solid electrolyte membrane, the flexibility is solid
State battery cathode and the second encapsulating film are sequentially placed to form the first laminated construction, complete to encapsulate to the laminated construction.
Optionally, the offer flexible solid anode, specifically includes:
It is coated with and/or is sprayed positive electrode in plus plate current-collecting body, obtains flexible solid anode；
The offer flexible solid battery cathode, specifically includes:
It is coated with and/or is sprayed negative electrode material in negative current collector, obtains flexible solid battery cathode.
Optionally, the plus plate current-collecting body comprises at least one of the following: aluminium, nickel or aluminium alloy；
The positive electrode comprises at least one of the following: LiFePO4, cobalt acid lithium, nickel-cobalt-manganese ternary lithium, lithium sulfur metal
Object, lithium sulfide or elemental sulfur.
Optionally, the negative current collector comprises at least one of the following: copper or its alloy；
The negative electrode material comprises at least one of the following: lithium metal and alloy, natural graphite, artificial graphite, MCMB, CNT
Or graphene
Optionally, described that ultrathin flexible solid electrolyte membrane is prepared by chemical vapour deposition technique, it specifically includes:
Ultrathin flexible solid electrolyte membrane is prepared using ultrahigh vacuum or aumospheric pressure cvd method.
Optionally, the ultrathin flexible solid electrolyte membrane comprises at least one of the following: inorganic solid electrolyte film has
Machine composite solid electrolyte film.
Optionally, the inorganic solid electrolyte film comprises at least one of the following: oxide solid electrolyte membrane or vulcanization
Object solid electrolyte membrane；Wherein,
The oxide solid electrolyte membrane comprises at least one of the following: Ca-Ti ore type, NaSiCON type, LiSiCON type or
LiPON type；
The sulfide solid electrolyte membrane comprises at least one of the following: P2S5、SiS2、B2S3Or Li4-xA1-xBxS4Wherein,
A is comprised at least one of the following: Ge, Si, and B is comprised at least one of the following: P, A1, Zn.
Optionally, the organic composite solid dielectric film comprises at least one of the following: polyethylene oxide, polyacrylonitrile,
Kynoar, polymethyl methacrylate, polypropylene oxide, Vingon or single-ion polymer.
Optionally, the thickness of the ultrathin flexible solid electrolyte membrane is not more than 200 microns.
Optionally, described by the first encapsulating film, the flexible solid anode, the ultrathin flexible solid electrolyte
Film, the flexible solid battery cathode and the second encapsulating film are sequentially placed to form laminated construction, and complete to the laminated construction
At encapsulation, specifically include:
First encapsulating film, the flexible solid anode, the ultrathin flexible solid electrolyte membrane, the flexibility is solid
State battery cathode and the second encapsulating film to form laminated construction by being sequentially placed from top to bottom；
By heat-seal technique by the flexible solid anode, the ultrathin flexible solid electrolyte membrane, described soft
Property solid state battery cathode is packaged between first encapsulating film and second encapsulating film.
Optionally, first encapsulating film and second flexible encapsulating film are clad aluminum plastic film.
The application provides a kind of flexible solid battery, uses aforementioned any method to prepare, comprising: successively
The first encapsulating film, flexible solid anode, the ultrathin flexible solid electrolyte membrane, flexible solid battery cathode and the placed
Two encapsulating films.
The application also provides a kind of preparation method of flexible solid battery, comprising:
The flexible encapsulating film for having positive electrode material layer is provided；
The flexible encapsulating film for having negative electrode material layer is provided；
The flexible encapsulating film with positive electrode material layer and the flexible encapsulating film with negative electrode material layer are dried
Processing；
Ultrathin flexible solid electrolyte membrane is prepared by chemical vapour deposition technique；
By the flexible encapsulating film with positive electrode material layer, the ultrathin flexible solid electrolyte membrane and there is cathode
The flexible encapsulating film of material layer is sequentially placed to form the second laminated construction, completes to encapsulate to second laminated construction；Wherein, institute
Positive electrode material layer and the negative electrode material layer are stated towards the ultrathin flexible solid electrolyte membrane.
Optionally, the flexible encapsulating film of the offer with positive electrode material layer includes:
Clad aluminum plastic film is provided；
Positive electrode is sprayed and/or is coated on the aluminum plastic film；
It is described provide have negative electrode material layer flexible encapsulating film include:
Complex lithium alloy sheet is provided；
Negative electrode material is sprayed and/or is coated on the complex lithium alloy sheet
The application also provides a kind of flexible solid battery, and aforementioned any method is used to prepare, comprising: according to
The flexible encapsulating film with positive electrode material layer of secondary placement, the ultrathin flexible solid electrolyte membrane and have negative electrode material layer
Flexible encapsulating film.
Compared with prior art, the application has the following advantages:
Flexible solid battery is there is ultrathin flexible, solves the conductivity problems of solid solid interface, thickness
Generally at 200 microns hereinafter, have certain tensile strength, torsional strength and foldability, can easily with wearable product
Carry out compound matching；Preparation method is ultrathin flexible anode, ultrathin flexible cathode, ultrathin flexible dielectric film and ultra-thin
Flexible encapsulating film etc. is stacked in a certain way, and is packaged to obtain under certain condition.It can be by using difference just
Negative electrode material system is matched with dielectric film, obtains a variety of different types of ultrathin flexible solid state batteries.It is prepared
Ultrathin flexible consolidates that safety is also very high, lays the foundation for the preparation of ultrathin flexible power supply.
Detailed description of the invention
Fig. 1 is a kind of 5 layers of ultrathin flexible solid state battery preparation method flow chart provided in this embodiment；
Fig. 2 is a kind of 3 layers of ultrathin flexible solid state battery preparation method flow chart provided in this embodiment；
Fig. 3 is a kind of 5 layers of ultrathin flexible solid-state battery structure schematic diagram provided in this embodiment；
Fig. 4 is a kind of 3 layers of ultrathin flexible solid-state battery structure schematic diagram provided in this embodiment.
Specific embodiment
Many details are explained in the following description in order to fully understand the application.But the application can be with
Much it is different from other way described herein to implement, those skilled in the art can be without prejudice to the application intension the case where
Under do similar popularization, therefore the application is not limited by following public specific implementation.
Embodiment one
As shown in Figure 1, it illustrates 5 layers of one kind of the ultrathin flexible solid state battery preparation sides that the embodiment of the present application one provides
Method flow chart.The basic ideas of flow chart reaction subsequent embodiment.The flow chart simultaneous reactions go out such ultrathin flexible solid-state
The preparation method of battery.
It is carried out below by way of preparation method of the specific embodiment to ultrathin flexible solid state battery provided by the present application detailed
Introduction and explanation.
As shown in Figure 1, the ultrathin flexible solid state battery the preparation method is as follows:
Step S101 is coated with and/or sprays positive electrode in plus plate current-collecting body and obtains flexible solid anode；
The flexible solid anode includes plus plate current-collecting body and positive electrode；Wherein, the plus plate current-collecting body includes
Following at least one: aluminium, nickel or aluminium alloy；The positive electrode comprises at least one of the following: LiFePO4, cobalt acid lithium, nickel cobalt
Manganese ternary lithium, lithium sulfur metal compound, lithium sulfide or elemental sulfur；In the present embodiment, the plus plate current-collecting body is aluminium foil, described
Positive electrode uses currently more popular nickelic ternary material.
In the present embodiment, plus plate current-collecting body selects the aluminium foil of 20 μ m thicks, and positive electrode selects nickelic ternary material.?
In this step, nickelic ternary material and conductive agent and binder are proportionally prepared into slurry, above-mentioned slurry is coated on institute
It states and prepares the flexible solid anode on aluminium foil.
Step S102 is coated with and/or sprays negative electrode material in negative current collector and obtains flexible solid battery cathode；
The flexible solid battery cathode includes negative current collector and negative electrode material；Wherein, the negative current collector includes
Following at least one: copper or its alloy；The negative electrode material comprises at least one of the following: lithium metal and alloy, natural graphite, people
Make graphite, MCMB, CNT or graphene；In the present embodiment, the negative current collector is copper foil, and the negative electrode material is adopted
With the artificial graphite material of the graphene of addition about 1%.
In the present embodiment, negative current collector selects the copper foil of 25 μ m thicks, and negative electrode material selects the graphite of addition about 1%
The artificial graphite material of alkene；Using same method, by the artificial graphite material of the graphene of addition about 1% and conductive agent and glue
Knot agent is proportionally prepared into slurry, and above-mentioned slurry is coated on the copper foil and prepares the flexible solid battery cathode.
It should be noted that can be carried out by using different positive and negative electrode material systems and ultrathin flexible solid electrolyte membrane
Matching, obtains a variety of different types of ultrathin flexible solid state batteries.The embodiment of the present invention flexible solid anode with it is described
The selection of flexible solid cell negative electrode material is not limited to this, for selecting other materials as the flexible solid anode
Also belong to the application's as long as selection rationally can be used for the technical program with the flexible solid cell negative electrode material
Protection scope.
Step S103, by the graphene of the aluminium foil of the nickelic ternary material slurry of coating and the coating addition about 1%
The copper foil of artificial graphite material slurry be dried.
Step S104 prepares LiPON ultrathin flexible solid electrolyte membrane using ultra-high vacuum CVD method.
The ultrathin flexible solid electrolyte membrane comprises at least one of the following: electrodeless solid electrolyte membrane or organic composite are solid
State dielectric film.The electrodeless solid electrolyte membrane comprises at least one of the following: oxide solid electrolyte membrane or sulfide are solid
State dielectric film；Wherein, the oxide solid electrolyte membrane comprises at least one of the following: Ca-Ti ore type, NaSiCON type,
LiSiCON type or LiPON type；The sulfide solid electrolyte membrane comprises at least one of the following: P2S5、SiS2、B2S3Or Li4- xA1-xBxS4, wherein A is comprised at least one of the following: Ge, Si, and B is comprised at least one of the following: P, A1, Zn.The organic composite is solid
State dielectric film comprises at least one of the following: polyethylene oxide, Kynoar, polymethyl methacrylate, is gathered polyacrylonitrile
Propylene oxide, Vingon or single-ion polymer.
In this embodiment, the ultrathin flexible solid electrolyte membrane is to be prepared using ultra-high vacuum CVD method
LiPON ultrathin flexible solid electrolyte membrane；First encapsulating film and the second encapsulating film are three layers of clad aluminum of 40 micron thickness
Plastic film.It should be noted that the technical solution of the application is usually applied to the ultrathin flexible solid electrolyte membrane and the envelope
The selection of the material of film is filled, but its application field is not limited thereto, and meets the ultrathin flexible solid state electrolysis for other
The selection of the material of plasma membrane and the encapsulating film, it can be used for the technical program, obtain same beneficial effect.
Step S104 concrete operations are described below:
Deposition reaction device is purged with argon gas first, the vacuum degree of reaction chamber is modulated 10 by vacuum controller-4Pa, will
530 DEG C of temperature modulation；
Lithium phosphate is subjected to nanosizing pretreatment；
The mixed gas of nitrogen and argon gas is passed through reaction chamber；
Nanosizing lithium phosphate (the 2 < n of preheating will be passed through with argon gasNitrogen:nLithium phosphate< 3) it is sent into reaction chamber, adjust reaction chamber
Temperature and pressure reacts reactant sufficiently；
Side reaction product phosphorous oxides, oxidate for lithium etc. are exported in reaction process；
It is continually fed into argon gas, reaction temperature is reduced after 1.5 to 2 hours of sustained response to 100 degree or so, is in area
80cm2Titanium alloy film forming substrate obtains LiPON ultrathin flexible solid electrolyte membrane.
Step S105 surpasses aluminium foil, the LiPON of first encapsulating film, the nickelic ternary material slurry of coating
Thin flexible solid dielectric film, the copper foil of artificial graphite material slurry of graphene of the coating addition about 1% and described
Second encapsulating film is placed in sequence forms the first laminated construction.
Step S106, in the low moisture vacuum (- 0.1MPa) ring of high-cleanness, high and water content less than 1% for being lower than 100ppm
In border, the laminated construction is completed to encapsulate using heat sealing machine.
It should be noted that in the present embodiment, step S101 and step S102, step S103 and step S104 are without successive
Sequentially, on the performance of prepared flexible solid battery without influence.
As shown in figure 3, it illustrates prepared by the ultrathin flexible solid state battery preparation method provided according to the present embodiment one
5 layers of one kind of ultrathin flexible solid-state battery structure schematic diagram
Including the first encapsulating film 301, flexible solid anode 302, the ultrathin flexible solid electrolyte membrane being sequentially placed
303, flexible solid anode 304 and the second encapsulating film 305.
The ultrathin flexible solid state battery has the characteristics that ultrathin flexible, and thickness general control is within 200 microns, most
Big 500 microns reachable, preferably 100 microns hereinafter, compound matching easily can be carried out with wearable product；Compared to not by external force
The case where stretching and reversing, the ultrathin flexible battery can bear to stretch the tensile strength for increasing 50-100% and torsion 50-
Without will cause the change of overall performance after 200% torsional strength；In addition to this, the ultrathin flexible solid state battery has certain
Bendable folding endurance, 0-179 ° of doubling can be born without influencing overall performance.Its good performance is no less than Current commercial
Lithium ion battery.
Ultrathin flexible solid state battery of the thickness of ipsilateral tab at 95 μm is finally made using the above method.It is measured, it should
The capacity of ultrathin flexible solid state battery about 30mAh, voltage platform 3.7V can carry out about 120 ° of bending without influencing performance.It is real
Test the result shows that, the ultrathin flexible solid state battery has good conductive capability and flexible.
Embodiment two
As shown in Fig. 2, it illustrates another 3 layers ultrathin flexible solid state battery systems that the embodiment of the present application two provides
Preparation Method flow chart.The flow chart equally reacts the basic ideas of subsequent embodiment.The flow chart also reflects such super simultaneously
The preparation method of thin flexible solid battery.
Below by way of specific embodiment to the preparation method of another ultrathin flexible solid state battery provided by the present application
It is introduced and illustrates.
As shown in Fig. 2, the other ultrathin flexible solid state battery the preparation method is as follows:
Step S201 is coated with and/or sprays the positive electrode in clad aluminum plastic film；
In the present embodiment, positive electrode selects polysulfide material.In this step, by polysulfide and conductive agent with
Binder is proportionally prepared into slurry, and above-mentioned slurry is sprayed on composite aluminium plastic film.
Step S202 is coated with and/or sprays the negative electrode material on complex lithium alloy sheet,
It in step, is omitted on complex lithium alloy sheet and is coated with and/or sprays the negative electrode material, directly adopt 15 μm
The lithium alloy thin slice of thickness.
It should be noted that since clad aluminum plastic film and compound lithium alloy not can be used as positive and negative electrode current collector material respectively
Selection, while lithium alloy is also a kind of negative electrode material, and clad aluminum plastic film and compound lithium alloy play afflux in the present embodiment
The effect of body and encapsulating film, therefore the slurry of positive and negative electrode material is directly applied to clad aluminum plastic film and compound lithium alloy respectively
On be equivalent to positive and negative electrode.It therefore can be by using different positive and negative electrode material systems and the progress of ultrathin flexible solid electrolyte membrane
Match, obtains a variety of different types of ultrathin flexible solid state batteries.The embodiment of the present invention flexible solid anode with it is described soft
Property solid state battery negative electrode material selection it is not limited to this, for select other materials as the flexible solid anode with
The flexible solid cell negative electrode material, as long as selection rationally can be used for the technical program, also belong to the guarantor of the application
Protect range.
The clad aluminum plastic film of above-mentioned spraying polysulfide slurry is dried step S203.
Step S204 prepares Kynoar ultrathin flexible solid electrolyte membrane using aumospheric pressure cvd method.
Deposition reaction device is purged with argon gas first, the argon atmosphere of 100kPa is kept, adjusts the temperature to 260 DEG C；
Kynoar is melted in 210 DEG C of heating or more；
Kynoar after thawing is passed through reaction chamber, increases temperature to after about 350 DEG C, control argon stream is quick
Circulation makes Kynoar that fine droplet boiling-like be presented；
Be passed through lithium metal solution, make Kynoar present fine droplet and lithium metal solution with two kinds of fine droplet shapes into
Row sufficiently reaction；
After 1.5 to 2 hours of sustained response, reduces temperature and by-product and unreacting substance is discharged, in tungsten alloy substrate
On obtain Kynoar ultrathin flexible solid electrolyte membrane.
Step S205, above-mentioned two layers of clad aluminum plastic film, the Kynoar for being stained with polysulfide coating is ultra-thin soft
Property solid electrolyte membrane and the lithium alloy thin slice place in sequence formed the second laminated construction.Wherein, more vulcanizations are stained with
The side of the clad aluminum plastic film of object coating is towards Kynoar ultrathin flexible solid electrolyte membrane.
Step S206, in the low moisture vacuum (- 0.1MPa) ring of high-cleanness, high and water content less than 1% for being lower than 100ppm
In border, second laminated construction is completed to encapsulate using heat sealing machine.
It should be noted that in the present embodiment, step S202, step S203 and step S204 are without sequencing, to institute
The performance of the ultrathin flexible solid state battery of preparation is without influence.
As shown in figure 4, it illustrates prepared by the ultrathin flexible solid state battery preparation method provided according to the present embodiment two
3 layers of one kind of ultrathin flexible solid-state battery structure schematic diagram
Two layers of the clad aluminum plastic film 401, the Kynoar that are stained with polysulfide coating including being sequentially placed are ultra-thin
Flexible solid dielectric film 402 and the lithium alloy thin slice 403.
It is understood that the choosing to positive and negative pole material in this present embodiment and ultrathin flexible solid electrolyte membrane material
It selects not limited to this, for selecting other materials as preparing the ultrathin flexible solid state battery, as long as selection is rationally, belongs to
In the range of the application protection.
Using the above method, ultrathin flexible solid state battery of the thickness of ipsilateral tab out at 87 μm is finally made.Through measuring,
The capacity of the ultrathin flexible solid state battery about 12mAh, voltage platform 2.2V can carry out 60% longitudinal stretching without influence property
Energy.The experimental results showed that the ultrathin flexible solid state battery has good conductive capability and flexibility.
It should be noted that in the absence of conflict, the structure and method and embodiment in embodiment one of the application
Structure in two can be combined with each other with method.
Although the application is disclosed as above with preferred embodiment, it is not for limiting the application, any this field skill
Art personnel are not departing from spirit and scope, can make possible variation and modification, therefore the guarantor of the application
Shield range should be subject to the range that the claim of this application defined.
Claims (15)
1. a kind of preparation method of flexible solid battery characterized by comprising
Flexible solid anode is provided；
Flexible solid battery cathode is provided；
The flexible solid anode and the flexible solid battery cathode are dried；
Ultrathin flexible solid electrolyte membrane is prepared by chemical vapour deposition technique；
By the first encapsulating film, the flexible solid anode, the ultrathin flexible solid electrolyte membrane, flexible solid electricity
Pond cathode and the second encapsulating film are sequentially placed to form the first laminated construction, complete to encapsulate to the laminated construction.
2. preparation method according to claim 1, which is characterized in that the offer flexible solid anode, it is specific to wrap
It includes:
It is coated with and/or is sprayed positive electrode in plus plate current-collecting body, obtains flexible solid anode；
The offer flexible solid battery cathode, specifically includes:
It is coated with and/or is sprayed negative electrode material in negative current collector, obtains flexible solid battery cathode.
3. preparation method according to claim 2, which is characterized in that the plus plate current-collecting body comprises at least one of the following:
Aluminium, nickel or aluminium alloy；
The positive electrode comprises at least one of the following: LiFePO4, cobalt acid lithium, nickel-cobalt-manganese ternary lithium, lithium sulfur metal compound, lithium
Sulfide or elemental sulfur.
4. preparation method according to claim 2, which is characterized in that the negative current collector comprises at least one of the following:
Copper or its alloy；
The negative electrode material comprises at least one of the following: lithium metal and alloy, natural graphite, artificial graphite, MCMB, CNT or stone
Black alkene.
5. preparation method according to claim 1, which is characterized in that it is described prepared by chemical vapour deposition technique it is ultra-thin soft
Property solid electrolyte membrane, specifically includes:
Ultrathin flexible solid electrolyte membrane is prepared using ultrahigh vacuum or aumospheric pressure cvd method.
6. preparation method according to claim 5, which is characterized in that the ultrathin flexible solid electrolyte membrane includes following
It is at least one: inorganic solid electrolyte film or organic composite solid dielectric film.
7. preparation method according to claim 6, which is characterized in that the inorganic solid electrolyte film include it is following at least
It is a kind of: oxide solid electrolyte membrane or sulfide solid electrolyte membrane；Wherein,
The oxide solid electrolyte membrane comprises at least one of the following: Ca-Ti ore type, NaSiCON type, LiSiCON type or
LiPON type；
The sulfide solid electrolyte membrane comprises at least one of the following: P2S5、SiS2、B2S3Or Li4-xA1-xBxS4Wherein, A includes
Following at least one: Ge, Si, B are comprised at least one of the following: P, A1, Zn.
8. preparation method according to claim 6, which is characterized in that the organic composite solid dielectric film includes following
At least one: polyethylene oxide, Kynoar, polymethyl methacrylate, polypropylene oxide, gathers inclined chloroethene at polyacrylonitrile
Alkene or single-ion polymer.
9. preparation method according to claim 6, which is characterized in that the thickness of the ultrathin flexible solid electrolyte membrane is not
Greater than 200 microns.
10. preparation method according to claim 1, which is characterized in that described by the first encapsulating film, flexible solid electricity
Pond anode, the ultrathin flexible solid electrolyte membrane, the flexible solid battery cathode and the second encapsulating film are sequentially placed shape
It completes to encapsulate at laminated construction, and to the laminated construction, specifically include:
By the first encapsulating film, the flexible solid anode, the ultrathin flexible solid electrolyte membrane, flexible solid electricity
Pond cathode and the second encapsulating film to form laminated construction by being sequentially placed from top to bottom；
It is by heat-seal technique that the flexible solid anode, the ultrathin flexible solid electrolyte membrane, the flexibility is solid
State battery cathode is packaged between first encapsulating film and second encapsulating film.
11. preparation method according to claim 10, which is characterized in that first encapsulating film and second flexibility
Encapsulating film is clad aluminum plastic film.
12. a kind of flexible solid battery being prepared according to claim 1 to 11 any claim, feature exist
In, comprising: the first encapsulating film, flexible solid anode, ultrathin flexible solid electrolyte membrane, the flexible solid electricity being sequentially placed
Pond cathode and the second encapsulating film.
13. a kind of preparation method of flexible solid battery characterized by comprising
The flexible encapsulating film for having positive electrode material layer is provided；
The flexible encapsulating film for having negative electrode material layer is provided；
The flexible encapsulating film with positive electrode material layer and the flexible encapsulating film with negative electrode material layer are dried；
Ultrathin flexible solid electrolyte membrane is prepared by chemical vapour deposition technique；
By the flexible encapsulating film with positive electrode material layer, the ultrathin flexible solid electrolyte membrane and there is negative electrode material
The flexible encapsulating film of layer is sequentially placed to form the second laminated construction, completes to encapsulate to second laminated construction；Wherein, it is described just
Pole material layer and the negative electrode material layer are towards the ultrathin flexible solid electrolyte membrane.
14. the preparation method of the 3 flexible solid batteries according to claim 1, which is characterized in that described provide has positive material
The flexible encapsulating film of the bed of material includes:
Clad aluminum plastic film is provided；
Positive electrode is sprayed and/or is coated on the aluminum plastic film；
It is described provide have negative electrode material layer flexible encapsulating film include:
Complex lithium alloy sheet is provided；
Negative electrode material is sprayed and/or is coated on the complex lithium alloy sheet.
15. a kind of flexible solid battery prepared using claim 13 or 14 characterized by comprising the tool being sequentially placed
There are the flexible encapsulating film, the ultrathin flexible solid electrolyte membrane and the flexible package with negative electrode material layer of positive electrode material layer
Film.
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| CN110085916A (en) * | 2019-03-26 | 2019-08-02 | 合肥国轩高科动力能源有限公司 | A kind of flexible lithium ion battery and preparation method thereof for wearable device |
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