CN110518283A - Solid state secondary battery and its preparation process, electric car - Google Patents
Solid state secondary battery and its preparation process, electric car Download PDFInfo
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- CN110518283A CN110518283A CN201910864852.8A CN201910864852A CN110518283A CN 110518283 A CN110518283 A CN 110518283A CN 201910864852 A CN201910864852 A CN 201910864852A CN 110518283 A CN110518283 A CN 110518283A
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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
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
- H01M2300/0085—Immobilising or gelification of electrolyte
-
- 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
Abstract
The invention discloses a kind of solid state secondary battery and its preparation processes, electric car, are related to solid state cell technology field.Solid state secondary battery includes: the solid electrolyte layer between negative electrode layer, the anode layer and negative electrode layer and anode layer opposed with negative electrode layer；Anode layer includes plus plate current-collecting body and anode active material layer, and anode active material layer is adjacent with solid electrolyte layer；Gel polymer coating has been provided independently between negative electrode layer and solid electrolyte layer, between anode active material layer and solid electrolyte layer.The present invention alleviates existing all-solid lithium-ion battery interfacial instability, the technical issues of large interface Resistance Maximum degree constrains its energy density and power density, the present invention improves interfacial instability between electrode material and SSE and higher interface resistance and interfacial gap problem physically by the integral structure of polymer coating and positive and negative pole material and solid electrolyte, improves the chemical property of all-solid-state battery well.
Description
Technical field
The present invention relates to solid state cell technology fields, in particular to a kind of solid state secondary battery and its preparation work
Skill, electric car.
Background technique
What commercialized battery mostly used is flammable liquid electrolyte, between the electrolyte and lithium metal in electrolyte
Deep reaction can generate undesirable side reaction, so that the consumption of lithium and Li dendrite be caused to generate, reduce battery security, in turn
Lead to the generation of fire and catastrophic failure.It can using solid electrolyte (Solid state electrolytes, SSE) material
To avoid the use of flammable liquid, the generation of Li dendrite is hindered, to alleviate the above problem.
The ionic conductivity of current solid electrolyte may be up to 10-2S/cm has further pushed pushing away for solid electrolyte
Wide and application.But SSE and electrode material interface are usually unstable in all-solid-state battery, this unstable interface is often drawn
Biggish interface resistance is played, the promotion of battery performance is seriously constrained, limits its commercial applications.Document
J.Am.Chem.Soc.2016,138,9385-9388. it is reported in a kind of by polymer/ceramic electrolyte/polymer multi-layer
Structure designs improved all-solid-state battery, and (electrode material is respectively Li and LiFePO4), the coulombic efficiency of cyclic process is improved,
But the Modification design by physically stacking can not be fully solved its interface problem, also have to the promotion of battery performance
Limit.
It is therefore desired to provide a kind of new all-solid-state battery, it is able to solve at least one of above problem.
In view of this, the present invention is specifically proposed.
Summary of the invention
One of the objects of the present invention is to provide a kind of solid state secondary batteries, can alleviate in existing all-solid-state battery
The problem of interfacial gap, interface resistance are big, interfacial instability and lithium dendrite growth.
The second object of the present invention is to provide a kind of preparation process of above-mentioned solid state secondary battery, and process is simple, just
In industrialized production.
The third object of the present invention is to provide a kind of electric car, including above-mentioned solid state secondary battery or above-mentioned complete solid
Solid state secondary battery made from the preparation process of state secondary cell.
In order to realize above-mentioned purpose of the invention, the following technical scheme is adopted:
In a first aspect, the present invention provides a kind of solid state secondary batteries comprising: negative electrode layer and the negative electrode layer pair
The solid electrolyte layer between anode layer and the negative electrode layer and the anode layer set；Anode layer includes plus plate current-collecting body
And anode active material layer, the anode active material layer are adjacent with the solid electrolyte layer；
It is provided independently between negative electrode layer and solid electrolyte layer, between anode active material layer and solid electrolyte layer
There is gel polymer coating.
Preferably, on the basis of technical solution provided by the invention, the negative electrode layer is metal or alloy paillon.
Preferably, on the basis of technical solution provided by the invention, the negative electrode layer includes negative current collector and cathode
Active material layer, the anode active material layer are in contact with the gel polymer coating；
Preferably, the negative electrode active material of anode active material layer includes lithium titanate cathode material, carbon based negative electrodes material, nitride
One or more of negative electrode material or oxide cathode material.
Preferably, on the basis of technical solution provided by the invention, the positive-active material of the anode active material layer
Material includes one or more of carbon material, metal oxide, sulphur or sulfide.
Preferably, on the basis of technical solution provided by the invention, the solid electrolyte packet of the solid electrolyte layer
The fast ion for including the fast-ionic conductor of lithium, the fast-ionic conductor of sodium, the fast-ionic conductor of potassium, the fast-ionic conductor of magnesium or zinc is led
Body；
Preferably, solid electrolyte includes that sulfide solid electrolyte, solid oxide electrolyte or conducting polymer are solid
One or more of body electrolyte；
Preferably, solid oxide electrolyte includes LiPON type, Ca-Ti ore type, NASICON type, LISICON type or pomegranate
One or more of stone-type solid electrolyte；
Preferably, conductive solid polymer electrolyte includes polyphenyl, polyaniline, polypyrrole, polythiophene, polymethylacrylic acid
One or more of methyl esters, polyacrylonitrile, polyethylene glycol oxide, Kynoar or polyvinyl chloride.
Preferably, on the basis of technical solution provided by the invention, the gelatin polymer of gel polymer coating includes
Biasfluoroethylene-hexafluoropropylene, polyethylene glycol oxide, polyacrylonitrile, polymethyl methacrylate, polyamide, polyethylene glycol, poly- ammonia
Ester, polyethylene terephthalate, polybutylene terephthalate, polystyrene, polybutadiene, polytetrafluoroethylene (PTFE), polysulfide rubber
Glue, butadiene-styrene rubber, Styrene-Butadiene-Styrene Block Copolymer, ethylene-vinyl acetate copolymer, ethylene polycyclic oxygen second
Alkane, polyimides, polycarbonate, polyvinylidene fluoride, polyaniline, polyether sulfone, cellulose acetate, polylactic acid, gathers polyvinyl alcohol
One of caprolactone, polytrimethylene carbonate, polyethylene terephthalate or polylactide glycolate copolymer are several
Kind.
Second aspect, the present invention provides a kind of preparation processes of above-mentioned solid state secondary battery, comprising the following steps:
Gelatin polymer and solvent are mixed into interface modification slurry, interface modification slurry is independently uniformly overlayed on into anode
The surface of active material layer and negative electrode layer is stacked, suppressed and is dried with solid electrolyte layer when not being completely dried, obtained
Solid state secondary battery.
The present invention also provides the preparation processes of another above-mentioned solid state secondary battery, comprising the following steps:
Gelatin polymer and solvent are mixed into interface modification slurry, interface modification slurry is uniformly overlayed on into solid electrolyte
Layer it is two-sided, stacked, suppressed and dried with anode active material layer and negative electrode layer when not being completely dried, obtained all solid state
Secondary cell.
Preferably, on the basis of technical solution provided by the invention, the preparation process of solid state secondary battery, including with
Lower step:
Gelatin polymer and solvent are mixed into interface modification slurry, interface modification slurry is independently uniformly overlayed on into anode
The surface of active material layer and anode active material layer, when not being completely dried with solid electrolyte layer stacked, suppress and
It is dry, obtain solid state secondary battery；Or,
Gelatin polymer and solvent are mixed into interface modification slurry, interface modification slurry is uniformly overlayed on into solid electrolyte
Layer it is two-sided, stacked, suppressed and dried with anode active material layer and anode active material layer when not being completely dried, obtained
To solid state secondary battery.
Preferably, on the basis of technical solution provided by the invention, the solvent includes organic solvent and/or inorganic molten
Agent preferably includes alcohols, ketone, nitrile, benzene class, acids, amine, sulfoxide type, acyl chloride, chlorinated hydrocarbons, carbon disulfide, liquid
One or more of carbon dioxide, liquid sulfur dioxide or water；Preferably include methanol, ethyl alcohol, acetone, acetonitrile, isopropanol, two
Methyl sulfoxide, chlorosulfuric acid, chloroform, N-Methyl pyrrolidone, ethylenediamine, formic acid, benzene, carbon disulfide, carbon tetrachloride, liquefied ammonia, lemon
One or more of lemon acid, hydrazine hydrate, water, sulfuric acid, hydrogen fluoride, liquid carbon dioxide or liquid sulfur dioxide；
Preferably, the solvent is the mixed solvent of ethyl alcohol and acetone, and the volume ratio of ethyl alcohol and acetone is 1:1-1:10.
The third aspect, the present invention provides a kind of electric cars, including above-mentioned solid state secondary battery or above-mentioned all solid state
Solid state secondary battery made from the preparation process of secondary cell.
Compared with the prior art, the invention has the following beneficial effects:
(1) present invention between electrode material and solid electrolyte by being arranged gel polymer coating, gelatin polymer
Coating has compared to the smaller Young's modulus of solid electrolyte, i.e. polymer coating has certain flexibility, promotes two phase boundaries
The contact in face and the raising of binding force reduce the gap between electrode material and solid electrolyte layer and high interface resistance,
And interface is stabilized, inhibit the side reaction that may occur between the two, be conducive to the growth for inhibiting Li dendrite, gelatin polymer applies
The integral structure of layer and positive and negative pole material and solid electrolyte alleviates the physics between existing all-solid-state battery median surface
The problem of gap, high interface resistance, interfacial instability and Li dendrite, has more excellent chemical property.
(2) the gel polymer coating material that all-solid-state battery of the present invention uses be easy to get, environmental protection, simple production process, at
This is low, can effectively reduce interface resistance.
Detailed description of the invention
In order to illustrate more clearly of the technical solution of the specific embodiment of the invention, specific embodiment will be described below
Needed in attached drawing be briefly described.It should be evident that the accompanying drawings in the following description is some implementations of the invention
Mode for those of ordinary skill in the art without creative efforts, can also be according to these attached drawings
Obtain other attached drawings.
Fig. 1 is the structural schematic diagram of the solid state secondary battery of one embodiment of the present invention；
Fig. 2 is the structural schematic diagram of the solid state secondary battery of another embodiment of the present invention.
Diagram: 1- negative electrode layer；11- negative current collector；12- anode active material layer；2- gel polymer coating；3- solid
Electrolyte layer；4- anode layer；41- plus plate current-collecting body；42- anode active material layer.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
The conventional products that can be obtained by commercially available purchase.
According to the first aspect of the invention, a kind of solid state secondary battery is provided comprising: negative electrode layer and cathode
Solid electrolyte layer between layer opposed anode layer and negative electrode layer and anode layer；Anode layer includes plus plate current-collecting body and just
Pole active material layer, anode active material layer are adjacent with solid electrolyte layer；Between negative electrode layer and solid electrolyte layer, anode it is living
Gel polymer coating has been provided independently between property material layer and solid electrolyte layer.
The type of solid state secondary battery is not construed as limiting, all solid state lithium ion secondary cell is can be, is also possible to it
The solid state secondary battery of his ion, such as all-solid sodium ion secondary cell, full-solid potassium ion secondary cell, all solid state magnesium
Ion secondary battery or all solid state zinc ion secondary cell etc..
Negative electrode layer
Negative electrode layer (cathode, negative electrode tab) can be negative current collector and anode active material layer integral structure, can also be with
It is negative electrode layer include anode active material layer on negative current collector and negative current collector.
In some embodiments, it when negative electrode layer is negative current collector and anode active material layer integral structure, bears
Pole layer is metal or alloy paillon, and typical but non-limiting is, for example, aluminium foil or alloy foil etc..
In some embodiments, when negative electrode layer includes negative current collector and anode active material layer, negative electrode active material
The bed of material is mainly made of negative electrode active material, can additionally containing can be used for all-solid-state battery negative electrode layer known conductive agent and/
Or binder.
Negative electrode active material conventional in secondary cell, including but not limited to cathode of lithium material can be used in negative electrode active material
Material, carbon based negative electrodes material, nitride negative electrode material or oxide cathode material etc..
Lithium titanate cathode material refers to the metal active material containing lithium, including lithium metal and its alloy, such as LixAl、LixSi or
LixPb etc.；Carbon based negative electrodes material refers to the material containing carbon, such example include hard carbon, soft carbon, mesocarbon microbeads (MCMB) or
Highly oriented pyrolytic graphite (HOPG) etc.；Nitride negative electrode material includes metal nitride (such as Cu3N、CrN、Ge3N4、Li3-
xCoxN or Li3FeN2Deng) or non-metal nitride (such as SiN or VN etc.)；Oxide cathode material includes metal oxide (example
Such as Al2O3、TiO2、In2O3、Li4Ti5O12、LixMoO2、LixWO2、LiNiVO4、SnAlxOyOr nonmetal oxide (such as SiOx
Deng).
Anode layer
Anode layer includes the anode active material layer on plus plate current-collecting body and plus plate current-collecting body, and anode active material layer is main
It being made of positive electrode active materials, the known positive active material for all-solid-state battery can be used in positive electrode active materials, including
But be not limited to carbon material, metal oxide, sulphur or sulfide etc..
Typical but non-limiting carbon material is, for example, activated carbon or graphite etc.；Metal oxide includes binary or ternary gold
Belong to oxide, typical but non-limiting is, for example, LiCoO2、LiNiO2、LiMn2O4、LiCo1/3Ni1/3Mn1/3O2、LiFePO4Or
V2O5Deng；Typical but non-limiting sulfide is, for example, TiS2、FeS2、SnS2Or CuS2Deng.
Anode active material layer can also additionally contain for improving the conductive agent of electrical conductance, for bonding positive active material
Binder, or the thickener being added as needed.
Plus plate current-collecting body and negative current collector are preferably electronic conductor.The material of plus plate current-collecting body illustratively includes
Aluminium, aluminium alloy, stainless steel, nickel or titanium etc., preferably aluminum or aluminum alloy.The material of negative current collector illustratively include aluminium, copper,
Copper alloy, stainless steel, nickel or titanium etc., preferably copper or copper alloy.
Solid electrolyte layer
Solid electrolyte layer is the layer containing solid electrolyte, is not construed as limiting to solid electrolyte, and all solid state electricity can be used
The existing known solid electrolyte in pond.
Solid electrolyte is also known as fast-ionic conductor (ion conductor), and being described as ion can be in solid electrolyte freely
Migration, is not construed as limiting the ion conductor type of solid electrolyte, can be the fast-ionic conductor of lithium, i.e., using lithium ion as load
Stream, the fast-ionic conductor of the fast-ionic conductor (using sodium ion as carrier), potassium that are also possible to sodium is (using potassium ion as load
Stream), the fast-ionic conductor of the fast-ionic conductor (using magnesium ion as carrier) of magnesium or zinc (using zinc ion as carrier).
The type of solid electrolyte is not construed as limiting, the solid electrolyte of existing type can be used, also include to difference
The electrolyte of type carries out the ion conductor after structure and component regulation improvement.Solid electrolyte includes inorganic solid electrolyte,
It also include organic polymer solid electrolyte, inorganic solid electrolyte mainly has sulfide (such as Li2S、SiS2Deng), oxide
(such as P2O5、B2O3、SiO2Or Li2O etc.), oxysulfide (such as LiS-SiS2The a small amount of Li of middle incorporation3PO4、LiAlO2Or
Li2SiO3Deng) and nitrogen oxides (such as LiPON, LiSiPON or LiSON) etc..
Sulfide solid electrolyte includes the Li of halogen doping2The Li of S-X binary system and/or halogen doping2S-MeS2-
P2S5Ternary system, halogen represent Cl, Br or I, and X represents P2S5、SiS2、GeS2、B2S3Or Al2S4, Me represent Si, Ge, Sn or
Al, as example, sulfide solid electrolyte can enumerate Li2S-SiS2、Li2S-P2S5-LiCl、Li2S-P2S5-H2S-LiCl、
LiI-Li2S-SiS2、LiI-Li2S-P2S5、Li2S-LiBr-P2S5、LiI-Li2S-P2O5、Li2S-P2S5-SiS2、LiI-Li3PO4-
P2S5、Li2S-Li2O-P2S5、Li2S-P2S5-SnS、Li2S-P2S5-Al2S3、Li2S-GeS2、Li2S-GeS2-ZnS、Li2S-
Ga2S3、Li2S-GeS2-P2S5、Li2S-GeS2-Ga2S3、Li2S-P2S5Or Li3PS4Deng.
The crystal form of solid oxide electrolyte is not construed as limiting, including but not limited to LiPON type (LiPON), perovskite
Type (ABO3Type, such as La0.55Li0.35TiO3), NASICON type (such as LiTi2P3O12), LISICON type (such as
Li3.5Zn0.25GeO4) or carbuncle type solid electrolyte (such as Li7La3 Zr2O12(Li6.5La3Zr1.75Te0.25O12), preferably
For garnet-type solid electrolyte.
Solid organic polymer electrolyte includes but is not limited to polyphenyl, polyaniline, polypyrrole, polythiophene, polymethyl
Sour methyl esters (PMMA), polyacrylonitrile (PAN), polyethylene glycol oxide (PEO), Kynoar (PVDF) or polyvinyl chloride (PVC) etc..
Solid electrolyte layer can also contain binder, and negative electrode layer or the binder that anode layer contains can be used.
The thickness of solid electrolyte layer is not construed as limiting, it is related with the structure of all-solid-state battery, preferably 0.01 μm-
10mm, more preferably 0.01-100 μm.
Gel polymer coating
Further include gel polymer coating in the structure of solid state secondary battery, negative electrode layer is separately set and is consolidated
(i.e. negative electrode layer connects with solid electrolyte layer between body electrolyte layer and between anode active material layer and solid electrolyte layer
Touching, anode active material layer is contacted with solid electrolyte layer, when negative electrode layer includes negative current collector and anode active material layer,
Anode active material layer is contacted with gel polymer coating).
Gel polymer coating refers to that the layer containing gelatin polymer, gelatin polymer refer to the high molecular polymerization in gel state
Object, the quasi polymer have certain flexibility, and Young's modulus is lower compared with solid electrolyte, the Young mould of illustrative gelatin polymer
Amount is 101~105MPa。
Gelatin polymer includes but is not limited to biasfluoroethylene-hexafluoropropylene (PVDF-HFP), polyethylene glycol oxide (PEO), gathers
Acrylonitrile (PAN), polyamide (PA), polyethylene glycol (PEG), polyurethane (PU), gathers to benzene polymethyl methacrylate (PMMA)
Dioctyl phthalate second diester, polystyrene (PS), polybutadiene (PB), polytetrafluoroethylene (PTFE) (PTFE), gathers polybutylene terephthalate
Sulphur rubber, butadiene-styrene rubber (SBR), Styrene-Butadiene-Styrene Block Copolymer (SBS), ethylene-vinyl acetate copolymer,
Ethylene polyethylene oxide, polyimides (Pi), polycarbonate (PC), polyvinylidene fluoride (PVDF), is gathered polyvinyl alcohol (PVA)
Aniline, polyether sulfone, cellulose acetate, polylactic acid (PLA), polycaprolactone (PCL), polytrimethylene carbonate (PTMC), poly- pair
Ethylene terephthalate (PET) or polylactide glycolate copolymer (PLGA) etc..
The thickness of gel polymer coating is not construed as limiting, it is preferable that the gel between negative electrode layer and solid electrolyte layer
The thickness of gel polymer coating between polymer coating and anode active material layer and solid electrolyte layer independently is
0.01-100 μm, preferably 0.01-10 μm.
As an implementation, the structural schematic diagram of solid state secondary battery is as shown in Figure 1, negative including what is stacked gradually
Pole layer 1, gel polymer coating 2, solid electrolyte layer 3, the gel polymer coating 2, (anode active material layer 42 of anode layer 4
With plus plate current-collecting body 41), wherein negative electrode layer 1 is metal or alloy paillon, while as negative electrode active material and negative current collector.
As another embodiment, the structural schematic diagram of solid state secondary battery is as shown in Fig. 2, include stacking gradually
Negative current collector 11, anode active material layer 12, gel polymer coating 2, solid electrolyte layer 3, gel polymer coating 2,
Anode active material layer 42 and plus plate current-collecting body 41.
The present invention between electrode material and solid electrolyte by being arranged gel polymer coating, gel polymer coating
With compared to the smaller Young's modulus of solid electrolyte, i.e. polymer coating has certain flexibility, reduces electrode material
Gap and high interface resistance between solid electrolyte layer, and interface is stabilized, inhibit the pair that may occur between the two
Reaction is conducive to the growth for inhibiting Li dendrite, the integrated knot of gel polymer coating and positive and negative pole material and solid electrolyte
Structure alleviates physical clearance, high interface resistance, interfacial instability and Li dendrite between existing all-solid-state battery median surface
The problem of, there is more excellent chemical property.
According to the second aspect of the invention, a kind of preparation process of solid state secondary battery is provided, comprising: by gel
Polymer and solvent are mixed into interface modification slurry, can be coated on the table of positive and negative anodes electrode material surface or solid electrolyte
Face, then stack with other structures and solid state secondary battery is made.
In some embodiments, when negative electrode layer is negative current collector and anode active material layer is integrated,
When i.e. solid state secondary battery has structure shown in Fig. 1, the preparation process of solid state secondary battery is the following steps are included: by gel
Polymer and solvent are mixed into interface modification slurry, and interface modification slurry is independently uniformly overlayed on to anode active material layer and is born
The surface of pole layer, is stacked, suppressed and is dried with solid electrolyte layer when not being completely dried, obtain all solid state secondary electricity
Pond；Alternatively, the preparation process of solid state secondary battery is the following steps are included: be mixed into interface modification for gelatin polymer and solvent
Interface modification slurry is uniformly overlayed on the two-sided of solid electrolyte layer by slurry, when not being completely dried and anode active material layer
It stacked, suppressed and is dried with negative electrode layer, obtain solid state secondary battery.
Solvent includes organic solvent and/or inorganic solvent, and type is not construed as limiting, including but not limited to alcohols, ketone, nitrile
Class, benzene class, acids, amine, sulfoxide type, acyl chloride, chlorinated hydrocarbons, carbon disulfide, liquid carbon dioxide, liquid sulfur dioxide or
Water etc.；As preferred embodiment, such as methanol, ethyl alcohol, acetone, acetonitrile, isopropanol, dimethyl sulfoxide, sulfonyl can be enumerated
Chlorine, chloroform, N-Methyl pyrrolidone, ethylenediamine, formic acid, benzene, carbon disulfide, carbon tetrachloride, liquefied ammonia, citric acid, hydrazine hydrate,
Water, sulfuric acid, hydrogen fluoride, liquid carbon dioxide or liquid sulfur dioxide etc..Preferably, solvent is molten for the mixing of ethyl alcohol and acetone
Agent, and the volume ratio of ethyl alcohol and acetone is 1:1-1:10, such as 1:1,1:2,1:3,1:4,1:5,1:6,1:7,1:8,1:9 or 1:
10。
The ratio of gelatin polymer and solvent is not construed as limiting, and preferably gelatin polymer concentration is 0.5-1.5g/mL.
Preferably, the mode for being covered with gelatin polymer is not limited to coat, such as by spin coating, blade coating or can impregnate absorption
Etc. modes.It is preferred that being pre-processed to positive and negative electrode, cleaned up after cathode (or anode) polishing mechanical is flattened.
After not being completely dried Shi Zhicong and covering slurry to before being completely dried (and not being completely dried) any time, therewith
Opposite is to be completely dried, and refers to drying completely, i.e., solvent is volatilized completely (without solvent), is not completely dried i.e. also containing molten
Agent.
The preferred rolling of compacting.
In the preparation, interface modification slurry independently can uniformly be overlayed on anode active material layer and cathode by a kind of method
Layer surface (on one side), formed have polymer coating electrode material, then again with the other parts (solid electrolyte of battery
Film) it stacks, it assembles integral.Another method is that the surface (two-sided) of prepared solid electrolyte is coated with upper interface to change
Property slurry, form the two-sided solid electrolyte film with polymer coating, it is then (positive and negative with the other parts of battery again
Pole) it stacks, it assembles integral.
In some embodiments, when negative electrode layer includes negative current collector and anode active material layer, i.e., all solid state two
It is similar with the above method when primary cell has structure shown in Fig. 2, the preparation process of solid state secondary battery the following steps are included:
Gelatin polymer and solvent are mixed into interface modification slurry, interface modification slurry is independently uniformly overlayed on into positive electrode active materials
The surface of layer and anode active material layer, is stacked, suppressed and is dried with solid electrolyte layer when not being completely dried, obtained
Solid state secondary battery；Alternatively, the preparation process of solid state secondary battery is the following steps are included: gelatin polymer and solvent are mixed
Interface modification slurry is synthesized, interface modification slurry is uniformly overlayed on into the two-sided of solid electrolyte layer, be not completely dried Shi Yuzheng
Pole active material layer and anode active material layer are stacked, suppressed and are dried, and solid state secondary battery is obtained.
The generation type of inventive gel polymer coating is easy, all-solid-state battery simple production process, at low cost, entirely
The integral structure of battery can effectively reduce interface resistance.
As a kind of specific embodiment, the preparation process of solid state secondary battery the following steps are included:
(a) interface modification slurry is provided: gelatin polymer is added in solvent, is sufficiently mixed into and interface modification is uniformly made
Slurry；
(b) provide anode and cathode: anode includes plus plate current-collecting body and anode active material layer, and cathode includes negative pole currect collecting
Body and anode active material layer；And anode active material layer and anode active material layer are independently polished, mechanical pressing
And cleaning；
(c) interface modification slurry is independently overlying on anode active material layer by spin coating, blade coating or immersion suction type
With anode active material layer surface；
(d) it is stacked when not being completely dried with solid electrolyte layer, is rolled and dried after assembling is integral, cut out
Solid state secondary battery is obtained after cutting.
As another specific embodiment, the preparation process of solid state secondary battery the following steps are included:
(a) interface modification slurry is provided: gelatin polymer is added in solvent, is sufficiently mixed into and interface modification is uniformly made
Slurry；
(b) provide anode and cathode: anode includes plus plate current-collecting body and anode active material layer, and cathode includes negative pole currect collecting
Body and anode active material layer；And anode active material layer and anode active material layer are independently polished, mechanical pressing
And cleaning；
(c) solid electrolyte is formed a film by cold pressing or hot pressing, it is then spare after polishing treatment；
(d) interface modification slurry is overlying on the two-sided of solid electrolyte layer by spin coating, blade coating or immersion suction type；
(e) it is stacked when not being completely dried with anode active material layer and anode active material layer, is allowed to form three
Mingzhi's structure is rolled and is dried after assembling is integral, obtains solid state secondary battery after cutting.
It should be noted that, although above-mentioned steps are indicated with (a), (b), (c), but being not required for or imply must be according to this
Particular order executes these operations, these steps any can execute simultaneously or successively.
According to the third aspect of the present invention, a kind of electric car is provided, electric car includes above-mentioned all solid state secondary
Solid state secondary battery made from the preparation process of battery or above-mentioned solid state secondary battery.
Electric car is the automobile run as driving power by solid state secondary battery, due to of the invention all solid state
Secondary cell chemical property is outstanding, and therefore, electric car has advantage identical with solid state secondary battery and effect.
Invention is further described in detail combined with specific embodiments below.It is the preferred embodiment of the present invention below,
It should be pointed out that for those skilled in the art, without departing from the principles of the embodiments of the present invention, also
Several improvements and modifications can be made, these modifications and embellishments are also considered to be within the scope of the present invention.Each original of the present invention
Material can pass through commercially available acquisition.
Embodiment 1 makes all-solid lithium-ion battery
1, it prepares anode layer: weighing LiFePO4It is 1g with conductive black and Kynoar (mass ratio 7:2:1) gross weight
It is added in the N-Methyl pyrrolidone of 12mL and anode sizing agent is made, be coated on plus plate current-collecting body (the Al foil coated with carbon),
30min is dried at 100 DEG C on hot plate, forms anode layer；
2, it prepares negative electrode layer: weighing natural graphite and Kynoar (mass ratio 9:1) 1g is added to the N- first of 10mL
Negative electrode slurry is made in base pyrrolidones, is coated on negative current collector (copper foil), dries 30min at 100 DEG C on hot plate,
Form negative electrode layer；
3, prepare the electrode material of interface modification: the biasfluoroethylene-hexafluoropropylene (PVDF-HFP) for weighing 0.8g is added to
In 12mL ethyl alcohol and acetone (volume ratio 1:5) solvent, heating stirring at after uniform liquid separately electrode material (just
Pole layer and negative electrode layer) wherein one side on scratch film forming, tailored after 12h in vacuum oven in flakes；
4, it prepares the solid electrolyte of all-solid-state battery: selecting carbuncle type Li7La3Zr2O12It (LLZO) is solid electrolytic
Matter, solid electrolyte is cold-pressed it is blocking, it is stand-by after being processed by shot blasting to its surface；
5, it is assembled into all-solid-state battery: will have cated electrode material (anode layer or negative electrode layer) as lower layer, later
The solid electrolyte prepared is put on upper layer, places cated electrode material (negative electrode layer or anode in solid electrolyte upper layer
Layer), it is allowed to form sandwich structure, the battery after assembling is subjected to AC impedance (EIS) test, characterizes its interface resistance
Size.
Embodiment 2-20
Embodiment 2-20 difference from example 1 is that, the type of polymer for electrode material surface coating is not
Together.Battery after assembling is subjected to AC impedance and electrochemical property test according to the method for embodiment 1, as a result such as 1 institute of table
Show.
Table 1
Embodiment 21
1, it prepares anode layer: weighing LiFePO4, conductive carbon and Kynoar weigh 1g (mass ratio 8:1:1) altogether and be added
Anode sizing agent is made into 12ml N-Methyl pyrrolidone, is coated on plus plate current-collecting body (the Al foil coated with carbon), in hot plate
On at 100 DEG C dry 30min, form anode layer；
2, it prepares negative electrode layer: weighing natural graphite and Kynoar and be added to 10mL altogether heavy 1g (quality 8.5:1.5)
N-Methyl pyrrolidone in negative electrode slurry is made, be coated on negative current collector (Al foil), it is dry at 100 DEG C on hot plate
30min forms negative electrode layer；
3, it prepares the solid electrolyte of all-solid-state battery: selecting carbuncle type Li7La3Zr2O12It (LLZO) is solid electrolytic
Matter, it is stand-by after being processed by shot blasting to its surface after solid electrolyte cold pressing film forming；
4, prepare the preparation of interface modification coating: the PVDF-HFP for weighing 0.8g is added to 12mL ethyl alcohol and acetone (volume
Than in 1:5) solvent, heating stirring on solid electrolyte surface at two-sided blade coating film forming is carried out after uniform liquid, in vacuum
Disk is tailored into drying box after 12h；
5, assemble all solid state battery structure: by electrode material (anode layer or negative electrode layer) as lower layer, upper layer is put later
Upper tow sides all carry out the solid electrolyte of surface coated treatment, place electrode material (negative electrode layer in solid electrolyte upper layer
Or anode layer), it is allowed to form sandwich structure.
Embodiment 22-40
Embodiment 22-40 and embodiment 21 the difference is that, the type of polymer for electrode material surface coating
It is different.Battery after assembling is subjected to AC impedance and electrochemical property test according to the method for embodiment 1, as a result such as table 2
It is shown.
Table 2
Embodiment 41
1, it prepares anode layer: weighing LiFePO4, conductive carbon and Kynoar weigh 1g (mass ratio 9:1:1) altogether and be added
Anode sizing agent is made into 12ml N-Methyl pyrrolidone, is coated on plus plate current-collecting body (the Al foil coated with carbon), in hot plate
On at 100 DEG C dry 30min, form anode layer；
2, it prepares negative electrode layer: weighing natural graphite and Kynoar and be added to 10mL altogether heavy 1g (quality 8.5:1.5)
N-Methyl pyrrolidone in negative electrode slurry is made, be coated on negative current collector (Al foil), it is dry at 100 DEG C on hot plate
30min forms negative electrode layer；
3, it prepares the solid electrolyte of all-solid-state battery: selecting carbuncle type 78Li2S-22P2S5It (LPS) is solid electrolytic
Matter, it is stand-by after being processed by shot blasting to its surface after solid electrolyte cold pressing film forming；
4, prepare the preparation of interface modification coating: the PVDF-HFP for weighing 0.8g is added to 12mL ethyl alcohol and acetone (volume
Than in 1:5) solvent, heating stirring on solid electrolyte surface at two-sided blade coating film forming is carried out after uniform liquid, in vacuum
Disk is tailored into drying box after 12h；
5, assemble all solid state battery structure: by electrode material (anode layer or negative electrode layer) as lower layer, upper layer is put later
Upper tow sides all carry out the solid electrolyte of surface coated treatment, place electrode material (negative electrode layer in solid electrolyte upper layer
Or anode layer), it is allowed to form sandwich structure.
Embodiment 42-60
Embodiment 42-60 and embodiment 41 the difference is that, the type of polymer for electrode material surface coating
It is different.Battery after assembling is subjected to AC impedance and electrochemical property test according to the method for embodiment 1, as a result such as table 3
It is shown.
Table 3
Embodiment 61-70
Embodiment 61-70 and embodiment 41 the difference is that, the positive electrode of use is different.By the electricity after assembling
Pond carries out AC impedance and electrochemical property test according to the method for embodiment 1, and the results are shown in Table 4.
Table 4
Embodiment 71-80
Embodiment 71-80 and embodiment 41 the difference is that, the negative electrode material of use is different.By the electricity after assembling
Pond carries out AC impedance and electrochemical property test according to the method for embodiment 1, and the results are shown in Table 5.
Table 5
Embodiment 81-90
Embodiment 81-90 and embodiment 41 the difference is that, the solid electrolyte type of use is different.It will be assembled
Battery afterwards carries out AC impedance and electrochemical property test according to the method for embodiment 1, and the results are shown in Table 6.
Table 6
Comparative example 1-3
Comparative example 1-3 and embodiment 1, embodiment 21 and embodiment 41 the difference is that, applied without interface modification
Layer directly assembles anode layer, negative electrode layer and solid electrolyte.
Comparative example 4
The design of polymer/ceramic electrolyte/polymeric multilayer structure improves all-solid-state battery, and (electrode material is respectively Li
And LiFePO4)(J.Am.Chem.Soc.2016,138,9385-9388)。
Battery after assembling is subjected to AC impedance and electrochemical property test according to the method for embodiment 1, as a result such as
Shown in table 7.
Table 7
It can be seen that from above-mentioned test data with not plus compared with gel polymer coating, there is gel polymer coating knot
The interface resistance of the all-solid-state battery of structure significantly reduces, and is conducive to the promotion of the chemical property of battery.As it can be seen that coating of the present invention
The battery structure that modifying interface method obtains can alleviate the physical clearance between all-solid-state battery median surface, high interface electricity
The problem of resistance, interfacial instability and Li dendrite.Although illustrate and describing the present invention with specific embodiment, should realize
It arrives, many other change and modification can be made without departing from the spirit and scope of the present invention.It is, therefore, intended that
It in the following claims include all such changes and modifications belonged in the scope of the invention.
Claims (10)
1. a kind of solid state secondary battery, which is characterized in that the solid state secondary battery includes: negative electrode layer and the cathode
Solid electrolyte layer between layer opposed anode layer and the negative electrode layer and the anode layer；Anode layer includes anode collection
Fluid and anode active material layer, the anode active material layer are adjacent with the solid electrolyte layer；
It has been provided independently between negative electrode layer and solid electrolyte layer, between anode active material layer and solid electrolyte layer solidifying
Xanthan polymer coating.
2. solid state secondary battery described in accordance with the claim 1, which is characterized in that the negative electrode layer is metal or alloy foil
Piece.
3. solid state secondary battery described in accordance with the claim 1, which is characterized in that the negative electrode layer include negative current collector and
Anode active material layer, the anode active material layer are in contact with the gel polymer coating；
Preferably, the negative electrode active material of anode active material layer includes lithium titanate cathode material, carbon based negative electrodes material, nitride cathode
One or more of material or oxide cathode material.
4. according to the described in any item solid state secondary batteries of claim 1-3, which is characterized in that the anode active material layer
Positive electrode active materials include one or more of carbon material, metal oxide, sulphur or sulfide.
5. according to the described in any item solid state secondary batteries of claim 1-3, which is characterized in that the solid electrolyte layer
Solid electrolyte includes the fast-ionic conductor or zinc of the fast-ionic conductor of lithium, the fast-ionic conductor of sodium, the fast-ionic conductor of potassium, magnesium
Fast-ionic conductor；
Preferably, solid electrolyte includes sulfide solid electrolyte, solid oxide electrolyte or conductive solid polymer electricity
Solve one or more of matter；
Preferably, solid oxide electrolyte includes LiPON type, Ca-Ti ore type, NASICON type, LISICON type or carbuncle type
One or more of solid electrolyte；
Preferably, conductive solid polymer electrolyte includes polyphenyl, polyaniline, polypyrrole, polythiophene, poly-methyl methacrylate
One or more of ester, polyacrylonitrile, polyethylene glycol oxide, Kynoar or polyvinyl chloride.
6. according to the described in any item solid state secondary batteries of claim 1-3, which is characterized in that gel polymer coating coagulates
Xanthan polymer includes biasfluoroethylene-hexafluoropropylene, polyethylene glycol oxide, polyacrylonitrile, polymethyl methacrylate, polyamide, gathers
Ethylene glycol, polyurethane, polyethylene terephthalate, polybutylene terephthalate, polystyrene, polybutadiene, polytetrafluoro
Ethylene, polysulfide rubber, butadiene-styrene rubber, Styrene-Butadiene-Styrene Block Copolymer, ethylene-vinyl acetate copolymer, second
Alkene polyethylene oxide, polyvinyl alcohol, polyimides, polycarbonate, polyvinylidene fluoride, polyaniline, polyether sulfone, acetate fiber
Element, polylactic acid, polycaprolactone, polytrimethylene carbonate, polyethylene terephthalate or polylactide glycolate copolymer
One or more of.
7. a kind of preparation process of solid state secondary battery described in any one of claims 1-6, which is characterized in that including following
Step:
Gelatin polymer and solvent are mixed into interface modification slurry, interface modification slurry is independently uniformly overlayed on into positive-active
The surface of material layer and negative electrode layer is stacked, suppressed and is dried with solid electrolyte layer when not being completely dried, is obtained entirely solid
State secondary cell；Or,
Gelatin polymer and solvent are mixed into interface modification slurry, interface modification slurry is uniformly overlayed on into solid electrolyte layer
It is two-sided, it stacked, suppressed and is dried with anode active material layer and negative electrode layer when not being completely dried, obtained all solid state secondary
Battery.
8. the preparation process of solid state secondary battery according to claim 7, which comprises the following steps:
Gelatin polymer and solvent are mixed into interface modification slurry, interface modification slurry is independently uniformly overlayed on into positive-active
The surface of material layer and anode active material layer is stacked, suppressed and is dried with solid electrolyte layer when not being completely dried,
Obtain solid state secondary battery；Or,
Gelatin polymer and solvent are mixed into interface modification slurry, interface modification slurry is uniformly overlayed on into solid electrolyte layer
It is two-sided, it stacked, suppressed and is dried with anode active material layer and anode active material layer when not being completely dried, obtained complete
Solid secondary batteries.
9. according to the preparation process of the described in any item solid state secondary batteries of claim 7-8, which is characterized in that the solvent
Including organic solvent and/or inorganic solvent, alcohols, ketone, nitrile, benzene class, acids, amine, sulfoxide type, acyl chlorides are preferably included
One or more of class, chlorinated hydrocarbons, carbon disulfide, liquid carbon dioxide, liquid sulfur dioxide or water；Preferably include first
Alcohol, ethyl alcohol, acetone, acetonitrile, isopropanol, dimethyl sulfoxide, chlorosulfuric acid, chloroform, N-Methyl pyrrolidone, ethylenediamine, formic acid,
Benzene, carbon disulfide, carbon tetrachloride, liquefied ammonia, citric acid, hydrazine hydrate, water, sulfuric acid, hydrogen fluoride, liquid carbon dioxide or liquid dioxy
Change one or more of sulphur；
Preferably, the solvent is the mixed solvent of ethyl alcohol and acetone, and the volume ratio of ethyl alcohol and acetone is 1:1-1:10.
10. a kind of electric car, which is characterized in that the electric car includes described in any one of claims 1-6 all solid state
All solid state secondary electricity made from the preparation process of secondary cell or the described in any item solid state secondary batteries of claim 7-9
Pond.
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