CN109361015A - A kind of sulfide composite solid electrolyte and preparation method thereof, solid state battery - Google Patents
A kind of sulfide composite solid electrolyte and preparation method thereof, solid state battery Download PDFInfo
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- CN109361015A CN109361015A CN201811089944.5A CN201811089944A CN109361015A CN 109361015 A CN109361015 A CN 109361015A CN 201811089944 A CN201811089944 A CN 201811089944A CN 109361015 A CN109361015 A CN 109361015A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
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- 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
- H01M2300/0088—Composites
- H01M2300/0091—Composites in the form of mixtures
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- 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 present invention relates to sulfide composite solid electrolytes and preparation method thereof, solid state battery.Sulfide composite solid electrolyte of the invention is prepared with the raw material for preparing sulfide solid electrolyte matrix by poly- carbonic acid alkenyl esters or is prepared by poly- carbonic acid alkenyl esters and sulfide solid electrolyte matrix.Preparation method of the invention, include the following steps: S1, weigh the raw material or sulfide solid electrolyte matrix for preparing sulfide solid electrolyte matrix by certain quality, and it is mixed with the poly- carbonic acid alkenyl esters of certain mass, then it puts it into tophan box, solvent is added, mill ball is added, tophan box is sealed；S2, sealing tophan box rotation is driven, carries out centrifugal breaking, obtains slurry；S3, slurry is scratched to plate object, obtains sulfide composite solid electrolyte film after dry.Sulfide composite solid electrolyte provided by the invention uses poly- carbonic acid alkenyl esters for composite material, improves the ionic conductivity of sulfide composite solid electrolyte.
Description
Technical field
The present invention relates to a kind of sulfide composite solid electrolytes and preparation method thereof, solid state battery, belong to battery preparation
Technical field.
Background technique
Currently, the electrolyte of commercial li-ion battery is generally organic liquid, i.e. electrolyte, when in lithium ion battery appearance
When portion's short circuit or overheat, the electrolyte of this organic liquid is easy to cause the security risks such as thermal runaway, kindling.Solid electrolyte
With high security, voltage window mouth width, operating temperature section are wide, and good cycle, self-discharge rate are low, are easy to filming and small-sized
The advantage of change etc., corresponding solid state battery is then the important development direction of lithium battery.It then can be from root using solid electrolyte
The safety issue of battery is solved in sheet.
Solid electrolyte is divided into solid polyelectrolyte, inorganic solid electrolyte and composite solid electrolyte.Polymer
Solid electrolyte has excellent flexibility, can alleviate the volume expansion of interface under battery service condition, play stable interface
Effect.But solid polyelectrolyte ion conductivity is poor, voltage window is narrow, mechanical property is low and is difficult to inhibit lithium
Dendritic growth.Inorganic solid electrolyte can keep higher chemical stability, voltage window mouth width in wider temperature range,
High mechanical strength, wherein glass ceramics state sulfide electrolyte conductivity at room temperature with higher becomes most promising
One of electrolyte.
However, sulfide solid electrolyte flexibility is poor, preparation process is complicated, and that there are thickness is big for manufactured dielectric film,
The features such as flexibility is poor, and machinability is poor.And by composite means, obtained polymer/inorganic hybrid solid-state electrolyte is then
The advantages of having both above two material is the electrolyte for most having application prospect.
In polymer/sulfide composite solid electrolyte, polyether-based polymers (such as polyethylene oxide, PEO)/sulfide
Composite solid electrolyte is the emphasis of research.
However, causing sulphur or sulfide in the polymerization of polyethers the study found that sulphur and the ether-oxygen bond of polyethers react
Dissolution phenomena occurs in object, to can generate miscellaneous phase when sulfide composite electrolyte is prepared and formed a film, ionic conductivity is caused to drop
It is low.
Summary of the invention
(1) technical problems to be solved
In sulfide composite solid electrolyte in order to solve the prior art, sulphur or sulfide are in the polymer of polyethers
Dissolution phenomena occurs, and when sulfide composite solid electrolyte is prepared and formed a film, miscellaneous phase is generated, ionic conductivity is caused to reduce
Technical problem, the present invention provides a kind of sulfide composite solid electrolyte and preparation method thereof and containing the sulfide it is compound
The solid state battery of solid electrolyte.
(2) technical solution
In order to achieve the above object, the main technical schemes that the present invention uses include:
According to an aspect of the present invention, provide a kind of sulfide composite solid electrolyte, by poly- carbonic acid alkenyl esters with
The raw material for preparing sulfide solid electrolyte matrix is prepared or by poly- carbonic acid alkenyl esters and sulfide solid electrolyte base
Body is prepared.
Sulfide composite solid electrolyte according to the present invention, the poly- carbonic acid alkenyl esters include poly- ethylene carbonate, poly- carbon
At least one of acid propylene ester, poly- butylene and polycyclohexene.
Sulfide composite solid electrolyte according to the present invention, the molecular weight of the polypropylene carbonate is 100000~
500000。
Sulfide composite solid electrolyte according to the present invention, the mass fraction of the poly- carbonic acid alkenyl esters are 3~10 parts, system
The raw material of standby sulfide solid electrolyte matrix is 90~97 parts altogether；Or
The mass fraction of the poly- carbonic acid alkenyl esters is 3~10 parts, and sulfide solid electrolyte matrix is 90~97 parts.
Sulfide composite solid electrolyte according to the present invention, the sulfide composite solid electrolyte are film, film
With a thickness of 10~50 μm.
According to another aspect of the present invention, a kind of preparation method of sulfide composite solid electrolyte is provided comprising
Following steps:
S1, the raw material or sulfide solid electrolyte for preparing sulfide solid electrolyte matrix are weighed according to a certain mass ratio
Matrix, and mixed with the poly- carbonic acid alkenyl esters of certain mass, it then puts it into tophan box, certain solvent is added, adds
Mill ball seals tophan box；
S2, it drives the sealing tophan box to rotate, carries out centrifugal breaking, obtain slurry；
S3, slurry is scratched to plate object, obtains sulfide composite solid electrolyte film after dry.
Preparation method according to the present invention, in step sl: the poly- carbonic acid alkenyl esters include poly- ethylene carbonate, poly- carbon
At least one of acid propylene ester, poly- butylene, polycyclohexene；
The molecular weight of the polypropylene carbonate is 100000~500000；
The solvent includes at least one of 1,2- dichloroethanes, methyl phenyl ethers anisole and chloroform.
Preparation method according to the present invention, the mass fraction of the poly- carbonic acid alkenyl esters are 3~10 parts, the preparation vulcanization
The raw material of object solid electrolyte matrix is 90~97 parts altogether；Or
The mass fraction of the poly- carbonic acid alkenyl esters is 3~10 parts, and the sulfide solid electrolyte matrix is 90~97
Part.
Preparation method according to the present invention further includes step S4 after the step S3: by the sulfide solid-state electricity
Solve plasma membrane under the pressure of 10~50Mpa, in 80~300 DEG C of 5~10min of hot pressing；
Wherein, further preferred 100~220 DEG C of the temperature.
According to another aspect of the present invention, a kind of solid state battery, including electrolyte are provided, the electrolyte uses this hair
Bright sulfide composite solid electrolyte or the sulfide composite solid electrolyte obtained using method produced according to the present invention.
(3) beneficial effect
Sulfide composite solid electrolyte provided by the invention, due to using poly- carbonic acid alkenyl esters as composite material,
It does not include ether-oxygen bond, thus sulphur in sulfide solid electrolyte matrix or sulfide will not occur with poly- carbonic acid alkenyl esters it is anti-
It answers, therefore dissolution phenomena is not present, miscellaneous phase will not be generated, to improve the ionic conductance of sulfide composite solid electrolyte
Rate.
The preparation method of sulfide composite solid electrolyte provided by the invention, in a first aspect, due to using poly- carbonic acid
For alkenyl esters as composite material, sulphur or sulfide not comprising ether-oxygen bond, therefore in sulfide solid electrolyte matrix will not
It reacts with poly- carbonic acid alkenyl esters, therefore dissolution phenomena is not present, miscellaneous phase will not be generated, to improve composite solid electrolysis
The ionic conductivity of matter.
Second aspect after preparing sulfide composite solid electrolyte film, is further adopted in the preparation process in accordance with the present invention
With step S4, hot pressing is carried out to sulfide solid electrolyte membrane, within the temperature range of hot pressing, poly- carbonic acid alkenyl esters are pyrolyzed to be formed
Small molecule promotes sulfide solid electrolyte membrane volume contraction, improves the flexibility of film, increases the consistency of sample,
Simultaneously because the small molecule that pyrolysis is formed, viscosity is higher, therefore, reduces Intergranular impedance, to improve sulfide solid-state electricity
Solve the ionic conductivity of plasma membrane.
The third aspect, preparation method of the invention, compared with traditional solid phase method, eliminate ball milling, drying, heat treatment,
Processes, the simple processes such as tube sealing transfer are easy to realize industrial production.
Detailed description of the invention
Fig. 1 is the optical photograph of the film for the sulfide composite solid electrolyte that embodiment 1 is prepared.
Specific embodiment
It should be noted that in the absence of conflict, the feature in embodiment and embodiment in the application can
To be combined with each other.Below in conjunction with specific embodiment, the present invention will be described in detail.Below in conjunction with specific embodiment to this Shen
It please be described in further detail, these embodiments should not be understood as limiting the application range claimed.
According to an aspect of the present invention, provide a kind of sulfide composite solid electrolyte, by poly- carbonic acid alkenyl esters with
The raw material for preparing sulfide solid electrolyte matrix is prepared or by poly- carbonic acid alkenyl esters and sulfide solid electrolyte base
Body is prepared.
Sulfide composite solid electrolyte provided by the invention, due to using poly- carbonic acid alkenyl esters as composite material,
It does not include ether-oxygen bond, thus sulphur in sulfide solid electrolyte matrix or sulfide will not occur with poly- carbonic acid alkenyl esters it is anti-
It answers, therefore dissolution phenomena is not present, to improve the ionic conductivity of composite solid electrolyte.
Wherein, sulfide solid electrolyte matrix is the sulfide solid electrolyte of not compound other materials；It is logical
It crosses and prepares the raw material of sulfide solid electrolyte matrix and be prepared.The raw material for preparing sulfide solid electrolyte matrix is generally
Li2S and P2S5, it is additionally preferred to it further comprise Al2S3、GeS2、SiS2And SnS2At least one of.
Sulfide composite solid electrolyte according to the present invention, poly- carbonic acid alkenyl esters include poly- ethylene carbonate, poly- carbonic acid third
At least one of enester, poly- butylene and polycyclohexene.
Poly- ethylene carbonate, polypropylene carbonate, poly- butylene and the polycyclohexene that the present invention selects are equal
Discord sulphur or sulfide react, and therefore, select these polymer can be to avoid the dissolution phenomena of sulfide, so as to mention
The ionic conductivity of high-sulfur compound composite solid electrolyte.
Sulfide composite solid electrolyte according to the present invention, the molecular weight of polypropylene carbonate are 100000~500000.
When the molecular weight for the polypropylene carbonate that the present invention selects is 100000~500000, molecular weight is relatively high,
Viscosity is larger, can make the composite solid electrolyte obtained when the polypropylene carbonate amount of addition is less that can form a film, wherein sulphur
The accounting of compound solid electrolyte matrix is opposite to be improved, to improve the ionic conductivity of sulfide composite solid electrolyte.
Wherein, the molecular weight of polypropylene carbonate is typical but without limitation preferably: 100000,150000,200000,
250000、300000、350000、400000、450000、500000。
Sulfide composite solid electrolyte according to the present invention, the mass fraction of poly- carbonic acid alkenyl esters are 3~10 parts, prepare sulphur
The raw material of compound solid electrolyte matrix is 90~97 parts altogether；Or
The mass fraction of poly- carbonic acid alkenyl esters is 3~10 parts, and sulfide solid electrolyte matrix is 90~97 parts.
Wherein, the mass fraction of poly- carbonic acid alkenyl esters be 3~10 parts, typical but non-limiting preferably 3 parts, 4 parts, 5 parts,
6 parts, 7 parts, 8 parts, 9 parts and 10 parts, the sulfide composite solid electrolyte that can have not only guaranteed can form a film, but also can guarantee it
Ionic conductivity with higher.Wherein prepare the raw material or sulfide solid electrolyte matrix of sulfide solid electrolyte matrix
It is typical but without limitation preferably 90,91,92,93,94,95,96,97 parts.
Sulfide composite solid electrolyte according to the present invention, sulfide composite solid electrolyte are film, the thickness of film
It is 10~50 μm.
Wherein, if the thickness of film is greater than 50 μm, the flexibility of film is deteriorated, and interface resistance becomes larger；If the thickness of film
Degree is less than 10 μm, and film is easily broken, and after it is used for battery, short circuit easily occurs for battery；Film with a thickness of 10~50 μm when,
Its flexibility is best, and interface resistance is smaller, and the comprehensive performance of film is best, wherein Typical non-limiting ground preferably 10um, 15um,
20um, 30um, 35um, 40um, 45um and 50um.
According to another aspect of the present invention, a kind of preparation method of sulfide composite solid electrolyte is provided comprising
Following steps:
S1, the raw material or sulfide solid electrolyte base for preparing sulfide solid electrolyte matrix are weighed by certain quality
Body, and mixed with the poly- carbonic acid alkenyl esters of certain mass, it then puts it into tophan box, certain solvent is added, adds and grinds
Abrading-ball seals tophan box；
S2, sealing tophan box rotation is driven, carries out centrifugal breaking, obtains slurry；
S3, slurry is scratched to plate object, obtains sulfide composite solid electrolyte film after dry.
The preparation method of sulfide composite solid electrolyte provided by the invention, on the one hand, due to using poly- carbonic acid alkene
Base ester does not include ether-oxygen bond as composite material, therefore sulphur in sulfide solid electrolyte matrix or sulfide will not be with
Poly- carbonic acid alkenyl esters react, therefore dissolution phenomena is not present, and will not generate miscellaneous phase, have both effectively increased composite solid electricity
The consistency of matter is solved, and reduces Intergranular impedance, to improve the ionic conductivity of composite solid electrolyte；On the other hand, originally
The preparation method of invention eliminates the processes such as ball milling, drying, heat treatment, tube sealing transfer, technique compared with traditional solid phase method
Simply, it is easy to realize industrial production.
In the preparation process in accordance with the present invention, sulfide solid electrolyte matrix is that the sulfide of not compound other materials is solid
State electrolyte；It is prepared by preparing the raw material of sulfide solid electrolyte matrix.Prepare sulfide solid electrolyte
Raw material generally preferably Li2S and P2S5, additionally, it is preferred that further comprising Al2S3、GeS2、SiS2And SnS2At least one of.?
In step S1, the preferred Li of sulfidic materials2S and P2S5, mixed by the molar ratio of 7:3 best.
In the preparation process in accordance with the present invention, in step sl, poly- carbonic acid alkenyl esters are preferably dry in 30 DEG C of vacuum before addition
It is dry for 24 hours, to remove moisture therein.
In step sl, whole operation crosses range request O2And H2O partial pressure is less than the closed glove box full of argon gas of 0.1ppm
Middle progress.Since sulfidic materials are more sensitive to water and oxygen, water partial pressure height can generate toxic H2S gas, therefore it is required that hand
Water and partial pressure of oxygen in casing is small as far as possible, can be by sulfidic materials to the sensitivity of water and oxygen as its partial pressure respectively less than 0.1ppm
Degree drops to lower.
In step s 2, any one of the material preferably polytetrafluoroethylene of tophan box, corundum, zirconium oxide, it is selected
Tophan box material is heat-resisting and does not react with raw material；Mill ball is zirconia ball.
In step s 2, sealing tophan box can be placed in centrifugal crusher by centrifugal breaking, first mix with low speed several
Minute, it is broken then to increase revolving speed progress high speed centrifugation；To obtain slurry.Wherein, low speed preferably 300~800rpm, low speed
The time of progress preferably 5~30min, high speed preferably 1000~2000rpm, the time being carried out at high speed preferably 10~90min.
A large amount of heat is generated to machine loss to avoid continuing shattering process, is preferably provided with the broken completion of high speed centrifugation
Afterwards, it is spaced 10min, then carries out centrifugal breaking experiment next time.
Preparation method according to the present invention, in step sl: poly- carbonic acid alkenyl esters include poly- ethylene carbonate, poly- carbonic acid third
At least one of enester, poly- butylene, polycyclohexene；
The molecular weight of polypropylene carbonate is 100000~500000；
Solvent includes at least one of 1,2- dichloroethanes, methyl phenyl ethers anisole and chloroform.
Poly- ethylene carbonate, polypropylene carbonate, poly- butylene and the polycyclohexene that the present invention selects,
Discord sulphur or sulfide react, and therefore, select these polymer can be to avoid the dissolution phenomena of sulfide, so as to mention
The ionic conductivity of high-sulfur compound composite solid electrolyte.
When the molecular weight for the polypropylene carbonate that the present invention selects is 100000~500000, molecular weight is relatively high,
Viscosity is larger, can make the composite solid electrolyte obtained when the polypropylene carbonate amount of addition is less that can form a film, wherein sulphur
The accounting of compound solid electrolyte matrix is opposite to be improved, to improve the ionic conductivity of sulfide composite solid electrolyte.
One of solvent of the invention preferably 1,2- dichloroethanes, methyl phenyl ethers anisole and chloroform, further preferred methyl phenyl ethers anisole,
Vapour pressure is lower, volatilizees slower, can make the surfacing of film forming.
Preparation method according to the present invention, the mass fraction of poly- carbonic acid alkenyl esters are 3~10 parts, prepare sulfide solid-state electricity
The raw material for solving matter matrix is 90~97 parts altogether；Or
The mass fraction of poly- carbonic acid alkenyl esters is 3~10 parts, and sulfide solid electrolyte matrix is 90~97 parts.
Wherein, the mass fraction of poly- carbonic acid alkenyl esters is 3~10 parts, the sulfide composite solid electricity that can have both guaranteed
Solution matter can form a film, and can guarantee its ionic conductivity with higher.
Preparation method according to the present invention further includes after step s 3 step S4: sulfide solid electrolyte membrane is existed
Under the pressure of 10~50Mpa, typical but preferred without limitation 10Mpa, 15Mpa, 20Mpa, 25Mpa, 30Mpa, 35Mpa,
40Mpa, 45Mpa, 50Mpa, at 80~300 DEG C, it is typical but preferably 80 DEG C non-limiting, 90 DEG C, 100 DEG C, 120 DEG C, 130 DEG C,
140℃、150℃、160℃、170℃、180℃、190℃、200℃、220℃、240℃、250℃、260℃、270℃、280
DEG C, 290 DEG C and 300 DEG C, hot pressing 5~10min, typical but preferred without limitation 5min, 6min, 7min, 8min, 9min and
10min。
Wherein, further preferred 100~220 DEG C of temperature.
In the preparation process in accordance with the present invention, after preparing sulfide composite solid electrolyte film, step S4 is further used,
Hot pressing is carried out to sulfide solid electrolyte membrane, within the temperature range of hot pressing, poly- carbonic acid alkenyl esters are pyrolyzed to form small molecule, promote
Make sulfide solid electrolyte membrane volume contraction, improve the flexibility of film, increases the consistency of sample, reduce crystal boundary
Impedance, to improve the ionic conductivity of sulfide solid electrolyte membrane.
The preferably poly- ethylene carbonate of poly- ethylene (propylene) carbonate, polypropylene carbonate, poly- butylene, polycyclohexene.
These substances get along well sulphur or sulfide reacts, and pyrolysis temperature is at 230 DEG C or so.
The hot pressing when hot pressing temperature is 100~220 DEG C, poly- ethylene (propylene) carbonate Partial digestion generate small molecule, on the one hand, mention
The high flexibility of sulfide composite solid electrolyte film, on the other hand enhances the ion conductance of composite solid electrolyte film.
When hot pressing temperature is higher than 220 DEG C, poly- ethylene (propylene) carbonate may be made to decompose completely, influence sulfide composite electrolyte
The flexible raising of film；But when hot pressing temperature is higher than 220 DEG C, sulfide composite solid electrolyte film can be from glassy transition
For glass ceramics state, to further increase the ion conductance of sulfide composite solid electrolyte.
According to another aspect of the present invention, a kind of solid state battery, including electrolyte are provided, electrolyte is using of the invention
Sulfide composite solid electrolyte or the sulfide composite solid electrolyte obtained using method produced according to the present invention.
In order to preferably explain the present invention, in order to understand, with reference to the accompanying drawing, by specific embodiment, to this hair
It is bright to be described in detail.
Embodiment 1
Preparation method according to the present invention, first progress step S1: it is weighed by certain quality and prepares sulfide solid-state electricity
The raw material of matter matrix is solved, and is mixed with the poly- carbonic acid alkenyl esters of certain mass, is then put it into tophan box, is added certain molten
Agent adds mill ball, seals tophan box.Concrete operations are as follows:
Wherein poly- carbonic acid alkenyl esters select polypropylene carbonate；The raw material for preparing sulfide solid electrolyte matrix is selected
Li2S and P2S5。
Li is weighed respectively2S、P2S5With polypropylene carbonate raw material in the tophan box of polytetrafluoroethylene (PTFE), Φ 10 is added and aoxidizes
Zirconium ball；Wherein, Li2S and P2S5Molar ratio is 7:3, (Li2S+P2S5): (molecular weight: 350000) mass ratio is polypropylene carbonate
94:6, ball material mass ratio are 5:1, and ratio of grinding media to material refers to the raw material ratio of mill ball and addition, that is, zirconia ball and addition
(Li2S、P2S5And polypropylene carbonate) mass ratio.In order to improve the dispersibility of raw material, mixing time is reduced, is added a small amount of
Organic solvent anhydrous anisole, additive amount are total mass of raw material 10%, are finally sealed tophan box, whole operation process is all being filled
It is carried out in the closed glove box of full Ar gas.
Then it carries out step S2: driving sealing tophan box rotation, carry out centrifugal breaking, obtain slurry；
Above-mentioned tophan box is placed into centrifugal crusher, first with 600rpm mixed on low speed 6min, then, increases revolving speed extremely
1600rpm carries out centrifugal breaking, and time 30min forms slurry.
Step S3 is carried out later, scratches slurry to plate object, obtains sulfide composite solid electrolyte film after dry.
Wherein, after the completion of being crushed, tophan box is transferred in glove box, the slurry in tophan box is crossed into titanium mesh screen,
Zirconia ball is separated, is then scratched on glass plate, air drying obtains sulfide solid electrolyte membrane, obtained solid electrolyte
Film is 45um.
Embodiment 2
The embodiment and 1 other parameters of embodiment are all the same, and difference place is only that, carry out step after step s 3
S4, by sulfide solid electrolyte membrane under the pressure of 10Mpa, in 180 DEG C of hot pressing 10min, obtained solid electrolyte membrane is
40um。
Embodiment 3
The other parameters of the embodiment and embodiment 2 are all the same, and difference place is only that, using sulfide solid electrolyte
Matrix is mixed with polypropylene carbonate.
Embodiment 4
The other parameters of the embodiment and embodiment 2 are all the same, difference place be only that, the poly- carbonic acid alkenyl esters used for
Poly- ethylene carbonate.
Embodiment 5
The other parameters of the embodiment and embodiment 2 are all the same, difference place be only that, the poly- carbonic acid alkenyl esters used for
Poly- butylene.
Embodiment 6
The other parameters of the embodiment and embodiment 2 are all the same, difference place be only that, the poly- carbonic acid alkenyl esters used for
Polycyclohexene.
Comparative example 1
The other parameters of the comparative example and embodiment 1 are all the same, the difference is that, polyethylene oxide substitutes poly- carbonic acid third
Enester.
Comparative example 2
The other parameters of the comparative example and embodiment 2 are all the same, the difference is that, polyethylene oxide substitutes poly- carbonic acid third
Enester.
Applicant carries out the sulfide composite solid electrolyte film being prepared in Examples 1 to 6, comparative example 1 and 2
Conductivity test, test result are as shown in table 1.
Test method is as follows:
It is measured using conductivity of the AC impedence method to sulfide composite solid electrolyte film.Argon is being full of before measurement
Obstructive type battery is assembled in the glove box of gas, and sulfide composite solid electrolyte film (CSE) is washed into the circle that diameter is 1cm
Piece is subsequently sandwiched between two stainless steel (SS) electrodes, is assembled into Stainless Steel/sulfide composite solid electrolyte film/Stainless Steel
(SS/CES/SS) measurement system.Ac impedance spectroscopy is carried out using electrochemical workstation CHI660C (Shanghai Chen Hua instrument company)
It tests, in test process, setting exchange perturbation amplitude is 5mV, and range of scanned frequencies is 100KHz~0.1Hz.Measurement system
Temperature range is 20~80 DEG C, every 5 DEG C of progress one-shot measurements.
Table 1
| Ionic conductivity (S cm-1)25℃ | |
| Embodiment 1 | 5.15×10-4S cm-1 |
| Embodiment 2 | 8.94×10-4S cm-1 |
| Embodiment 3 | 4.73×10-3S cm-1 |
| Embodiment 4 | 4.15×10-4S cm-1 |
| Embodiment 5 | 5.28×10-4S cm-1 |
| Embodiment 6 | 6.73×10-4S cm-1 |
| Comparative example 1 | 6.34×10-5S cm-1 |
| Comparative example 2 | 7.34×10-5S cm-1 |
Compared by embodiment 1 and the comparison of comparative example 1 and embodiment 2~6 and comparative example 2, as can be seen that using
The ionic conductivity for the sulfide composite solid electrolyte film that poly- carbonic acid alkenyl esters are prepared, than using polyethylene oxide system
Standby obtained sulfide composite solid electrolyte film ionic conductivity is high, or even improves an order of magnitude.
Thus, it is possible to illustrate, present invention employs poly- carbonic acid alkenyl esters as composite material, due to not including ether-oxygen bond,
Sulphur or sulfide in sulfide solid electrolyte matrix will not react with poly- carbonic acid alkenyl esters, and dissolution phenomena is not present,
Miscellaneous phase will not be generated, to improve the ionic conductivity of composite solid electrolyte.
It is compared by embodiment 1 and embodiment 2, it can be seen that preparation method according to the present invention, when further using heat
When pressing step, the ionic conductivity of sulfide composite solid electrolyte can be improved to a greater extent.
It is compared by embodiment 2 and embodiment 3, with comparative example 1 and 2, it can be seen that either using sulfide solid-state electricity
Matter matrix is solved, or uses and prepares sulfide solid electrolyte, it is compound with the progress of poly- carbonic acid alkenyl esters, sulfide can be improved
The ionic conductivity of composite solid electrolyte.
In addition, the optical photograph for the sulfide composite solid electrolyte film being prepared by embodiment 2, can also see
Out, which has good flexibility.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of sulfide composite solid electrolyte, which is characterized in that it is by poly- carbonic acid alkenyl esters and prepares sulfide solid-state
The raw material of electrolyte matrix is prepared or is prepared by poly- carbonic acid alkenyl esters and sulfide solid electrolyte matrix.
2. sulfide composite solid electrolyte according to claim 1, which is characterized in that the poly- carbonic acid alkenyl esters include
It is at least one of following:
Poly- ethylene carbonate, polypropylene carbonate, poly- butylene, polycyclohexene.
3. sulfide composite solid electrolyte according to claim 2, which is characterized in that point of the polypropylene carbonate
Son amount is 100000~500000.
4. sulfide composite solid electrolyte according to claim 1, which is characterized in that the matter of the poly- carbonic acid alkenyl esters
Measuring number is 3~10 parts, and the raw material for preparing sulfide solid electrolyte matrix is 90~97 parts altogether；Or
The mass fraction of the poly- carbonic acid alkenyl esters is 3~10 parts, and the sulfide solid electrolyte matrix is 90~97 parts.
5. sulfide composite solid electrolyte according to claim 1, which is characterized in that the sulfide composite solid electricity
Solution matter be film, the film with a thickness of 10~50 μm.
6. a kind of preparation method of sulfide composite solid electrolyte, which comprises the steps of:
S1, the raw material for preparing sulfide solid electrolyte matrix or sulfide solid electrolyte base are weighed according to a certain mass ratio
Body, and mixed with the poly- carbonic acid alkenyl esters of certain mass, it then puts it into tophan box, solvent is added, adds mill ball,
Seal tophan box；
S2, it drives the sealing tophan box to rotate, carries out centrifugal breaking, obtain slurry；
S3, slurry is scratched to plate object, obtains sulfide composite solid electrolyte film after dry.
7. preparation method according to claim 6, which is characterized in that the poly- carbonic acid alkenyl esters include poly- ethylene carbonate
At least one of ester, polypropylene carbonate, poly- butylene and polycyclohexene；
Preferably, the molecular weight of the polypropylene carbonate is 100000~300000；
Preferably, the solvent includes at least one of 1,2- dichloroethanes, methyl phenyl ethers anisole and chloroform.
8. preparation method according to claim 6, which is characterized in that the mass fraction of the poly- carbonic acid alkenyl esters be 3~
10 parts, the raw material for preparing sulfide solid electrolyte matrix is 90~97 parts altogether；Or
The mass fraction of the poly- carbonic acid alkenyl esters is 3~10 parts, and the sulfide solid electrolyte matrix is 90~97 parts.
9. according to any preparation method of claim 6~8, which is characterized in that further include step after the step S3
Rapid S4:
By the sulfide solid electrolyte membrane under the pressure of 10~50Mpa, in 80~300 DEG C of 5~10min of hot pressing,
Further preferred 100~220 DEG C of the temperature.
10. a kind of solid state battery, including electrolyte, the electrolyte is compound using the sulfide as described in Claims 1 to 5 is any
Solid electrolyte or the sulfide composite solid electrolysis obtained using the preparation method according to any one of claim 6-9
Matter.
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| CN112018458B (en) * | 2020-09-08 | 2021-11-30 | 长三角物理研究中心有限公司 | Sulfide-polymer composite solid electrolyte and preparation method and application thereof |
| CN114824448A (en) * | 2022-03-30 | 2022-07-29 | 广东马车动力科技有限公司 | Polypropylene carbonate-sulfide composite solid electrolyte membrane and preparation method and application thereof |
| CN115157518A (en) * | 2022-06-30 | 2022-10-11 | 蜂巢能源科技股份有限公司 | Preparation system of electrolyte membrane, preparation method of sulfide electrolyte membrane and application of sulfide electrolyte membrane |
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