CN109786822A - A kind of richness lithium anti-perovskite oxide composite electrolyte and its preparation method and application - Google Patents
A kind of richness lithium anti-perovskite oxide composite electrolyte and its preparation method and application Download PDFInfo
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- CN109786822A CN109786822A CN201811625967.3A CN201811625967A CN109786822A CN 109786822 A CN109786822 A CN 109786822A CN 201811625967 A CN201811625967 A CN 201811625967A CN 109786822 A CN109786822 A CN 109786822A
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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
- 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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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The present invention provides a kind of rich lithium anti-perovskite oxide composite electrolyte, the material of the richness lithium anti-perovskite oxide composite electrolyte includes polymer, lithium salts and filler, and the filler is rich lithium anti-perovskite oxide；Wherein, rich lithium anti-perovskite oxide structure formula general formula is Li3‑xHxOA1‑yBy, wherein A and B is halogens, 0≤x≤1,0≤y≤1.Ionic conductivity, the electrochemical window of composite polymer electrolyte can not only be improved using rich lithium anti-perovskite oxide electrolyte as filler, and it can increase the mechanical performance of composite electrolyte, reduce the interface impedance between electrolyte and lithium base cathode, the composite electrolyte made lithium ion conductivity with higher and good bending machinery performance, higher interface stability.
Description
Technical field
The present invention relates to new energy materials field more particularly to a kind of rich lithium anti-perovskite oxide composite electrolyte and its
Preparation method, a kind of all-solid-state battery and preparation method thereof.
Background technique
With the fast development of the industries such as electronics, information and new-energy automobile, new energy storage device has become scientific skill
The focus of art development, and the research and development of the solid lithium ion battery of high safety, large capacity is led as current new energy materials
The research hotspot in domain.Due to possessing, energy density is big, safety, long service life, operating voltage are high, environmental-friendly etc. many excellent
Point, solid lithium ion battery play more and more crucial effect in various fields.
Solid electrolyte is the critical material of solid ionic battery, and solid electrolyte is ion conductor, is generally required
Higher ionic conductivity, low electronic conductivity and low activation energy.Solid electrolyte is broadly divided into three classes: inoganic solids electricity
Xie Zhi, organic solid electrolyte and composite solid electrolyte.Different types of electrolyte has different advantage and disadvantage, inoganic solids
Electrolyte, also known as lithium fast-ionic conductor, are solid materials in the operating condition with high lithium ion conductivity, and tool is high
The advantages that safety, long service life, good ionic conduction performance and electrochemical stability, but its flexibility is poor, boundary
Interface impedance between impedance and electrolyte and electrode is big, and difficult processing limits its actual application.Organic solid electrolyte
It is divided into solid polymer electrolyte and gel polymer electrolyte.Solid polymer electrolyte is by lithium salts and polymer complex
At polymer electrolyte.Polymer Li-ion battery is electrode, electrolyte and diaphragm integral type structure of whole solid state, is easy to
Integrated assembly, security performance is high, but its bad mechanical strength, and conductivity is lower, limits its application.
Individually a kind of electrolyte is difficult to meet and be required, therefore, in addition to pure phase or single-phase above-mentioned inorganic or organic
Other than solid electrolyte, composite solid electrolyte is also had received widespread attention.Composite solid electrolyte mainly passes through will be inorganic
Solid electrolyte is added in organic solid electrolyte as filler, inorganic solid electrolyte on the one hand by the lithium from height from
Sub- seepage flow improves the lithium ion conductivity of polymer dielectric into polymeric matrix material, and what is on the other hand introduced consolidates
The body electrolyte granular material lift mechanical performance of composite electrolyte.Currently, composite solid polymer electrolyte majority is logical
Addition inorganic filler is crossed to be modified polymer dielectric.Composite solid polymer electrolyte includes that two kinds of inorganic lithium ions are led
Compound, the inorganic lithium ion conductor of compound, organic lithium ion conductor-lithium ion insulator-lithium ion insulator of body is compound,
Lithium ion insulator-lithium ion insulator is compound.But the composite solid electrolyte being prepared at present can not still have simultaneously
Standby high ionic conductivity, wide in range electrochemical window, good mechanical performance, lower interface impedance, higher stability
Etc. characteristics.
Summary of the invention
The purpose of the present invention is to provide a kind of rich lithium anti-perovskite oxide composite electrolytes and preparation method thereof, it is intended to
The electrolyte made is provided simultaneously with high ionic conductivity, wide in range electrochemical window, good mechanical performance, higher steady
It is qualitative.
Contain all solid state of rich lithium anti-perovskite oxide composite electrolyte another object of the present invention is to provide a kind of
Battery and preparation method thereof.
For achieving the above object, The technical solution adopted by the invention is as follows:
A kind of richness lithium anti-perovskite oxide composite electrolyte, the material of the richness lithium anti-perovskite oxide composite electrolyte
Material includes polymer, lithium salts and filler, and the filler is rich lithium anti-perovskite oxide.
The preparation method of rich lithium anti-perovskite oxide composite electrolyte, using solution casting method or melting pressure sintering preparation
Richness lithium anti-perovskite oxide composite electrolyte of the present invention.
And a kind of all-solid-state battery, the battery by be oppositely arranged positive plate, negative electrode tab and between positive plate and cathode
Electrolyte between piece is constituted, and the electrolyte uses above-mentioned rich lithium anti-perovskite oxide composite electrolyte or the electricity
The rich lithium anti-perovskite oxide composite electrolyte that the Xie Zhiwei above method is prepared, and the rich lithium anti-perovskite oxide
Composite electrolyte with a thickness of 1 μm~5cm.
The preparation method of all-solid-state battery, preparation method include the rich lithium anti-perovskite oxidation according to the preparation of above-mentioned preparation method
Object composite electrolyte；The rich lithium anti-perovskite oxide composite electrolyte heating melting is obtained rich lithium anti-perovskite oxide to answer
Close electrolyte solution；The rich lithium anti-perovskite oxide compound electrolyte solution is cast in positive plate or negative electrode tab, shape
At composite electrolyte membrane, the negative electrode tab being oppositely arranged or positive plate are sticked in the composite electrolyte membrane, is cooled to room temperature, obtains
Rich lithium anti-perovskite battery.
Rich lithium anti-perovskite oxide composite electrolyte prepared by the present invention, being includes polymer, lithium salts and filler, and
The filler is rich lithium anti-perovskite oxide.Wherein, it can not only be improved using rich lithium anti-perovskite oxide electrolyte as filler
The ionic conductivity of composite polymer electrolyte, electrochemical window, and can increase the mechanical performance of composite electrolyte, reduce electricity
Interface impedance between Xie Zhiyu lithium base cathode, the composite electrolyte made lithium ion conductivity with higher and good curved
Bent mechanical performance, higher interface stability.
The preparation method of rich lithium anti-perovskite oxide composite electrolyte in the present invention, specifically use solution casting method or
Melting any of pressure sintering, two kinds of preparation methods material mixing that only needs a person with the qualifications of a general is poured or hot pressing respectively again,
Preparation process is simple, easy to operate, and condition is controllable, is conducive to be mass produced.
The electrolyte of all-solid-state battery prepared by the present invention, the all-solid-state battery uses above-mentioned rich lithium anti-perovskite oxygen
Compound composite electrolyte, or the rich lithium anti-perovskite oxide composite electrolyte being prepared using the above method.Due to the richness
Lithium anti-perovskite oxide composite electrolyte conductivity height, electrochemical window mouth width, good mechanical property, interface impedance are small, so that this
The all-solid-state battery of invention has lesser interface impedance, excellent charge-discharge performance and high rate performance.
The present invention prepares battery, electrolyte and the electrode slice (anode of one side molten state using in-situ heat fusion-cast method
Piece and negative electrode tab) have preferable wellability, increase the contact area between electrolyte and electrode slice, solve electrolyte with
Contact problems between electrode；The electrolyte of another aspect molten state is directly poured on electrode slice, and preparation method is simple
It is easy, high production efficiency.
Detailed description of the invention
Fig. 1 is the LSV curve of rich lithium anti-perovskite composite electrolyte provided in an embodiment of the present invention.
Fig. 2 is the EIS curve of rich lithium anti-perovskite composite electrolyte provided in an embodiment of the present invention.
Fig. 3 is the SEM photograph of the section thickness of rich lithium anti-perovskite composite electrolyte provided in an embodiment of the present invention.
Specific embodiment
To keep the purpose, technical solution and technical effect of the embodiment of the present invention clearer, below in conjunction with of the invention real
The attached drawing in example is applied, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described implementation
Example is a part of the embodiment of the present invention, instead of all the embodiments.In conjunction with the embodiment in the present invention, ordinary skill
Personnel's every other embodiment obtained without creative efforts, shall fall within the protection scope of the present invention.
The present invention provides a kind of rich lithium anti-perovskite oxide composite electrolyte, and the richness lithium anti-perovskite oxide is compound
The material of electrolyte includes polymer, lithium salts and filler, and the filler is rich lithium anti-perovskite oxide.Specifically, described
Filler is rich lithium anti-perovskite oxide, and rich lithium anti-perovskite oxide is a kind of inorganic solid electrolyte, structural formula general formula
For Li3-xHxOA1-yBy, wherein A and B is halogens, 0≤x≤1,0≤y≤1.The advantages of rich lithium anti-perovskite oxide, wraps
Include: (1) material melting point is low, is conducive to direct built up membrane material and large-scale preparation and application；(2) activation energy is lower
And conductivity is higher, especially this structure adjustment for being easy to crystal structure and electronic structure, and carries out structure, component, crystal form tune
After control, material electric conductivity can be more than other existing solid electrolytes, and the conductivity of overage liquid electrolyte；(3) pole
Low electronic conductance；(4) density is small, light weight；(5) it is reacted with water and is decomposed into environmental-friendly lithium halide, and be easy to recycle benefit
With；(6) at low cost；(7) stablize with metal lithium electrode；(8) there is certain thermal stability；(9) close to the electrochemical window of 5V,
Meet the requirement of known high-voltage electrode material.Therefore, using rich lithium anti-perovskite oxide as inorganic filler, can well with
Polymer, lithium salts shell are merged, and are improved the conductivity of lithium ion, are widened its electrochemical window, change polymer property,
The mechanical performance of composite electrolyte is improved, while by fusion polymer and rich lithium anti-perovskite oxide, reducing interface resistance
It is anti-, improve the stability of composite electrolyte.
In embodiments of the present invention, the specific preferred Li of rich lithium anti-perovskite oxide3OCl、Li2OHCl、Li3OBr、
Li2OHBr、Li3OCl0.5Br0.5、Li3OCl0.7Br0.3、Li3OCl0.3Br0.7、Li2OHCl0.9F0.1、Li3OCl0.8F0.2Deng
Preferably, in the rich lithium anti-perovskite oxide composite electrolyte being prepared, rich lithium anti-perovskite oxide exists
Mass fraction in composite electrolyte are as follows: 1%~80%.
In a preferred embodiment of the invention, the rich lithium anti-perovskite oxide compound electric being prepared by solution casting method
Xie Zhi, the mass fraction of rich lithium anti-perovskite oxide in the electrolyte are 2%~80%, matter of the lithium salts in composite electrolyte
Measuring score is 5%~50%, and mass fraction of the polymer in composite electrolyte is 10%~80%.It is another preferably in the present invention
In embodiment, the rich lithium anti-perovskite oxide composite electrolyte being prepared by melting pressure sintering, rich lithium anti-perovskite oxygen
The mass fraction of compound in the electrolyte is 1%~80%, and mass fraction of the lithium salts in composite electrolyte is 1%~80%,
Mass fraction of the polymer in composite electrolyte is 10%~90%.
In rich lithium anti-perovskite oxide composite electrolyte, rich lithium anti-perovskite oxide can improve the machinery of electrolyte
Performance, and the crystallinity of polymer can be reduced, improve its conductivity；If the matter of rich lithium anti-perovskite oxide in the electrolyte
It is excessive to measure score, more than 80%, then composite electrolyte deteriorated flexibility, it is easier to be crushed；If content is too low, electrolysis can not be improved
The conductivity of matter causes its conduction bad；Lithium salts is as substance more important in electrolyte, with the increase of lithium salt content,
Ionic conductivity also gradually increases, if but lithium salt content is excessively high, lithium ion and anion will form neutral molecule, hinder lithium
The migration of ion reduces its conductivity, if how low lithium salt content is, ionic conductivity is low, the electrolytic conductivity being prepared
Difference, using effect are bad；Polymer has certain flexibility, is adapted to certain deformation, if polymer content is excessively high, makes
Standby obtained electrolyte flexibility is excessively high, is unfavorable for later period use；If polymer content is too low, the electrolyte being prepared is flexible
Too low, bad mechanical property is easily broken in use process.
Composite solid electrolyte is mainly by being added to organic solid electrolyte for inorganic solid electrolyte as filler
In, inorganic solid electrolyte one side improves polymerization into polymeric matrix material by the lithium ion seepage flow from height
The lithium ion conductivity of object electrolyte, the solid electrolyte particle material lift machinery of composite electrolyte on the other hand introduced
Performance.Specifically, the embodiment of the present invention using rich lithium anti-perovskite oxide as filler, be added to polymer, in lithium salts,
In, host component one of of the polymer as rich lithium anti-perovskite oxide composite electrolyte, since it is with good flexible
Property, battery can be made more resistant to shock and vibration, deformation, under abuse state (overcharge, short circuit, needle thorn etc.), will not be fired
The safety problems such as burning, explosion reduce electrolyte and electrode reaction activity, while formation and the electricity of Li dendrite can be effectively relieved
The hidden danger of pond internal short-circuit, and the cycle performance of battery can be improved.In a preferred embodiment of the invention, the polymer is selected from poly-
Caprolactone (PCL), polyethylene glycol oxide (PEO), polyacrylonitrile (PAN), polymethylacrylic acid (PMMA), Kynoar
(PVDF), the one or more of Kynoar-hexafluoropropene (PVDF-HFP).
Specifically, key component of the lithium salts as lithium cell electrolyte, is an important factor for determining electrolyte performance.At this
In invention preferred embodiment, the lithium salts is selected from lithium perchlorate (LiClO4) the corresponding adjustment of subscript full text, lithium hexafluoro phosphate
(LiPF6), hexafluoroarsenate lithium (LiAsF6), LiBF4 (LiBF4), bis trifluoromethyl sulfimide lithium (LiTFSI), double fluorine
Sulfimide lithium (LiFSI), trifluoromethyl sulfonic acid lithium (LiCF3SO3), di-oxalate lithium borate (LiBOB), difluorine oxalic acid boracic acid lithium
(LiDFOB) one or more.
Richness lithium anti-perovskite oxide composite electrolyte described in the embodiment of the present invention can be prepared by following methods.
Correspondingly, the embodiment of the invention provides a kind of preparation method of rich lithium anti-perovskite oxide composite electrolyte,
Specifically, using including that solution casting method and any of melting pressure sintering prepare the rich lithium anti-perovskite oxide compound electric
Xie Zhi.
In some embodiments, the rich lithium anti-perovskite oxide composite electrolyte is prepared using solution casting method.?
In specific embodiment, the process for preparing the rich lithium anti-perovskite oxide composite electrolyte using solution casting method is as follows:
S01: the polymer and the lithium salts are dissolved and obtain the first solution in organic solvent；
S02: rich lithium anti-perovskite oxide is added in first solution, is uniformly mixed and is formed the second solution；
S03: second solution is cast on substrate, and vacuum drying obtains rich lithium anti-perovskite oxide compound electric
Xie Zhi.
Specifically, above-mentioned solution casting method whole process operates in inert atmosphere glove box, operated in glove box
Can sufficiently starvation and other magazines pollution, guarantee that the electrolyte being prepared does not have impurity, will not be to battery performance
It impacts.In the preferred embodiment of the present invention, described glove box optional Mikrouna, Vigor, Etelux, Dellix.
Specifically, the polymer and the lithium salts dissolve and obtain first in organic solvent in above-mentioned S01 reaction step
Solution.In a preferred embodiment of the invention, the quality of the polymer and the lithium salts is (10-80): (5- than adding proportion
50), in the embodiment of the present invention, the mass ratio of the polymer and the lithium salts is particularly preferred as 3:1,4:1,5:1.Lithium salt content
When too low, the ionic conductivity of electrolyte is relatively low；When lithium salt content is excessively high, lithium ion and anion will form neutral molecule,
The migration for hindering lithium ion, reduces its conductivity.
Preferably, the organic solvent is that acetonitrile, succinonitrile etc. are any, based on the similar principle to mix, You Jirong
The addition of agent can sufficiently dissolve added polymer.In a preferred embodiment of the invention, can by polymer and lithium salts according to
It is re-dissolved in organic solvent after mass ratio mixing, further preferably, polymer can be first dissolved in organic solvent, then add
Lithium salts is added to be mixed.
In above-mentioned S02 reaction step, rich lithium anti-perovskite oxide is added in first solution, is uniformly mixed shape
At the second solution.Specifically, the additive amount of the richness lithium anti-perovskite oxide be 2wt% in composite electrolyte~
80wt%, the additive amount of rich lithium anti-perovskite oxide is 15wt% in a preferred embodiment of the invention.If the anti-calcium of the richness lithium
When titanium ore oxide additive amount is too low, the crystallinity of polymer cannot be effectively reduced, improve its conductivity；The excessive anti-calcium of rich lithium
Titanium ore oxide can make composite electrolyte deteriorated flexibility, be easily broken.Preferably, mixed mode may include the conventional skill such as stirring
Art means.Further, mixing the specific time is 2~48h, and temperature is 40~80 DEG C.
Specifically, second solution is cast on substrate in above-mentioned S03 reaction step, it is dried in vacuo, obtains richness
Lithium anti-perovskite oxide composite electrolyte.In a preferred embodiment of the invention, the substrate preferably polytetrafluoroethylene, polytetrafluoro
Ethylene is commonly referred to as " non-sticking lining " or " material easy to clean ".The spy that this material has antiacid alkali resistant, resists various organic solvents
Point is practically insoluble in all solvents.Meanwhile polytetrafluoroethylene (PTFE) has the characteristics that high temperature resistant, resistance to acid and alkali, anticorrosive.Therefore,
Generally select base material of the polyfluortetraethylene plate as lithium cell electrolyte.Specifically, by polymer, lithium salts, the anti-calcium of rich lithium
The mixed solution of titanium ore oxide is dried in vacuo after being cast in polyfluortetraethylene plate, and the temperature of the drying is 30~70
DEG C, the time is 12~72h.
In some embodiments, the rich lithium anti-perovskite oxide composite electrolyte is prepared using melting pressure sintering.?
In specific embodiment, the process for preparing the rich lithium anti-perovskite oxide composite electrolyte using melting pressure sintering is as follows:
D01: the rich lithium anti-perovskite oxide, the polymer are mixed with the lithium salts, heating melting shape
At electrolyte composite solution；
D02: on the first substrate by electrolyte composite solution casting, deviate from described first in electrolyte composite solution
The surface of substrate covers the second substrate, and hot pressing forms composite electrolyte membrane, is cooled to room temperature, obtains rich lithium anti-perovskite oxide
Composite electrolyte.
Specifically, above-mentioned melting pressure sintering whole process operates in inert atmosphere glove box, operated in glove box
Can sufficiently starvation and other magazines pollution, guarantee that the electrolyte being prepared does not have impurity, will not be to battery performance
It impacts.
Specifically, in above-mentioned steps D01, by the rich lithium anti-perovskite oxide, the polymer and the lithium salts
Adding proportion are as follows: (1~80): (10~90): (1~80).Wherein, when lithium salts additive amount is too low, the ionic conductance of electrolyte
Rate is relatively low；When lithium salts adding too much, lithium ion and anion will form neutral molecule, hinder the migration of lithium ion, reduce
Its conductivity.When rich lithium anti-perovskite oxide content is too low, the crystallinity of polymer cannot be effectively reduced, improve its conductance
Rate；Excessive rich lithium anti-perovskite oxide can make composite electrolyte deteriorated flexibility, be easily broken.Appropriate ratio can guarantee
Electrolyte had not only had high conductivity, but also the mechanical strength having had.
In the rich lithium anti-perovskite oxide composite electrolyte reacted according to above-mentioned adding proportion, the anti-calcium of rich lithium
Titanium ore oxide mass score is 1%~80%, and the mass fraction of polymer is 10%~90%, the matter of lithium salts in the electrolyte
Measuring score is 1%~80%.Specifically, rich lithium anti-perovskite oxide, polymer are mixed with lithium salts, the mixed method
Including the methods of hand-ground, mechanical stirring, ball grinding stirring, each component compound is handled using above-mentioned mixed method,
Can further comminuting matter partial size, the mixture partial size made is subtleer, while can guarantee that mixed material property is stablized.
Further, the heating temperature of the heating melting is 60~70 DEG C, and heating time is 2~48h.Currently preferred heating is molten
The specific heating temperature melted is 65 DEG C.
Specifically, in above-mentioned steps D02, in electrolyte composite solution away from the surface of first substrate covering second
Substrate, hot pressing form composite electrolyte membrane；In a preferred embodiment of the invention, in the heat-press step, temperature is 50~200
DEG C, pressure is 5~100 megapascal, and the time is 0.1~10 hour.Further, composite electrolyte membrane will be formed to be cooled to room temperature, is obtained
To rich lithium anti-perovskite oxide composite electrolyte.
The embodiment of the present invention provides a kind of all-solid-state battery, including be oppositely arranged positive plate, negative electrode tab and between anode
Electrolyte between piece and negative electrode tab is constituted.The electrolyte is above-mentioned rich lithium anti-perovskite oxide composite electrolyte.Due to
The all-solid-state battery contains rich lithium anti-perovskite oxide composite electrolyte described above, since the richness lithium anti-perovskite aoxidizes
Object composite electrolyte lithium ion conductivity is high, can achieve 10-6~10-3S cm-1；Electrochemical window mouth width property is stablized, electrification
Window is 4~7V；Electrolyte thickness is controllable, is 1 μm~5cm；Good mechanical property, interface impedance are small, so that of the invention is complete
Solid state battery has lesser interface impedance, excellent charge-discharge performance and high rate performance.
In a preferred embodiment of the invention, the positive plate active material is LiMn2O4 (LiMn2O4), cobalt acid lithium
(LiCoO2), LiFePO4 (LiFePO4), lithium nickelate (LiNiO2), iron manganese phosphate for lithium (LiFe0.2Mn0.8PO4), nickel ion doped
(LiNi0.5Mn1.5O4) or nickel-cobalt-manganese ternary material among it is one or more；The negative electrode tab active material is graphite, graphite
One of alkene, lithium anode, lithium alloy, silicon-carbon composite cathode, tin carbon compound cathode, lithium titanate are a variety of.
Correspondingly, including the following steps: the embodiment of the invention provides a kind of preparation method of all-solid-state battery
G01: rich lithium anti-perovskite oxide composite electrolyte is prepared according to any of the above-described preparation method；
G02: the rich lithium anti-perovskite oxide composite electrolyte heating melting is obtained into rich lithium anti-perovskite oxide and is answered
Close electrolyte solution；
G03: the rich lithium anti-perovskite oxide compound electrolyte solution is cast in positive plate or negative electrode tab, is formed
Composite electrolyte membrane；
G04: the negative electrode tab being oppositely arranged or positive plate are sticked in the composite electrolyte membrane, is cooled to room temperature, obtains richness
Lithium anti-perovskite battery.
Specifically, above-mentioned solution casting method whole process operates in inert atmosphere glove box, operated in glove box
Can sufficiently starvation and other magazines pollution, guarantee that the electrolyte being prepared does not have impurity, will not be to battery performance
It impacts.
In above-mentioned steps G01, the preparation method of the richness lithium anti-perovskite oxide composite electrolyte as it was noted above,
In order to save length, details are not described herein again.
In above-mentioned steps G02, the rich lithium anti-perovskite oxide composite electrolyte heating melting is obtained into the anti-calcium of rich lithium
Titanium ore oxide compound electrolyte solution；Preferably, the specific operating method of heating melting are as follows: by rich lithium anti-perovskite oxide
Composite electrolyte, which is put into crucible to be subsequently placed in heat on warm table, dissolves it completely；Preferred heating temperature is 50~200
℃。
In above-mentioned steps G03 and G04, the rich lithium anti-perovskite oxide compound electrolyte solution is cast in into anode
On piece or negative electrode tab, composite electrolyte membrane is formed；The negative electrode tab being oppositely arranged or positive plate are sticked in the composite electrolyte membrane,
Room temperature cooling obtains rich lithium anti-perovskite battery.It in a preferred embodiment of the invention, can be compound by rich lithium anti-perovskite oxide
Electrolyte solution casts in and forms composite electrolyte membrane in positive plate, then sticks negative electrode tab and waits for that its cooling can be prepared entirely
Solid-state anti-perovskite battery.Further, rich lithium anti-perovskite oxide compound electrolyte solution can be cast in negative electrode tab
Composite electrolyte membrane is formed, positive plate is then sticked and waits for that all solid state anti-perovskite battery can be prepared in its cooling.
Specifically, the dielectric film that the present invention is prepared with a thickness of 1 μm~5cm.The composite electrolyte membrane is controlled 1
μm~the suitable thickness of 5cm in, if thickness, less than 1 μm, obtained dielectric film is too thin, using the too thin electrolysis of thickness
The battery that matter assembles be easy to cause short circuit, causes battery quality bad；If thickness is greater than 5cm, obtained electrolyte
Film is too thick, can be bigger using the internal resistance of cell that the too thick electrolyte of thickness assembles, and is unfavorable for effective hair of battery performance
It waves.
The preparation method of the above all-solid-state battery is referred to as in-situ heat fusion-cast method, and this method and traditional lamination assemble
Method (by negative electrode tab, dielectric film, positive plate three level stack) is compared, and the application of in-situ heat fusion-cast method has primarily served two
The effect of aspect, the electrolyte and electrode slice (positive plate and negative electrode tab) of one side molten state have preferable wellability, increase
Contact area between electrolyte and electrode slice, solves the contact problems between electrolyte and electrode；On the other hand it melts
The electrolyte of state is directly poured on electrode slice, so that preparing all-solid-state battery becomes simple and easy.
Rich lithium anti-perovskite oxide composite electrolyte and preparation method thereof is illustrated below by way of multiple embodiments
Etc..
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Embodiment 1:
A kind of preparation method of richness lithium anti-perovskite oxide composite electrolyte, the richness lithium anti-perovskite oxide are compound
Electrolyte is prepared using solution casting method, specifically includes the following steps:
By polymer (PCL), lithium salts (LiTFSI) and rich lithium anti-perovskite oxide (Li3OCl0.6Br0.4) according to quality
Than being dissolved in organic solvent acetonitrile for 6:2:2, stirring in mixed solution is formed into homogeneous solution, is cast in polytetrafluoro
After dry 12h is placed in 60 DEG C of vacuum ovens in vinyl plate can form composite electrolyte.
Embodiment 2
A kind of preparation method of richness lithium anti-perovskite oxide composite electrolyte, the richness lithium anti-perovskite oxide are compound
Electrolyte is prepared using solution casting method, specifically includes the following steps: by polymer (PCL), lithium salts (LiFSI) and the anti-calcium of rich lithium
Titanium ore oxide (Li3OBr it is) that 5:1:1 is dissolved in organic solvent succinonitrile according to mass ratio, shape will be stirred in mixed solution
At homogeneous solution, being cast on polyfluortetraethylene plate after being placed in 60 DEG C of vacuum ovens dry 20h can be formed
Composite electrolyte.
Embodiment 3
A kind of preparation method of richness lithium anti-perovskite oxide composite electrolyte, the richness lithium anti-perovskite oxide are compound
Electrolyte is prepared using solution casting method, specifically includes the following steps:
By polymer (PEO), lithium salts (LiTFSI) and rich lithium anti-perovskite oxide (Li3OCl it is) 4 according to mass ratio:
1:1 is dissolved in organic solvent acetonitrile, and stirring in mixed solution is formed homogeneous solution, is cast on polyfluortetraethylene plate
After dry 12h is placed in 60 DEG C of vacuum ovens can form composite electrolyte.
Embodiment 4
A kind of preparation method of richness lithium anti-perovskite oxide composite electrolyte, the richness lithium anti-perovskite oxide are compound
Electrolyte is prepared using solution casting method, specifically includes the following steps:
By polymer (PEO), lithium salts (LiFSI) and rich lithium anti-perovskite oxide (Li3OCl0.5Br0.5) according to mass ratio
It is dissolved in organic solvent succinonitrile for 6:2:2, stirring in mixed solution is formed into homogeneous solution, is cast in polytetrafluoroethyl-ne
After dry 20h is placed in 60 DEG C of vacuum ovens on alkene plate can form composite electrolyte.
Embodiment 5
A kind of preparation method of richness lithium anti-perovskite oxide composite electrolyte, the richness lithium anti-perovskite oxide are compound
Electrolyte is prepared using melting pressure sintering, specifically includes the following steps:
By polymer (PCL), rich lithium anti-perovskite oxide (Li3OCl) with lithium salts (LiTFSI) according to certain quality
It is mixed into uniform compound than (6:2:2), is then placed in crucible and is heated to 200 DEG C of heat preservation 2h, finally by the mixed of heat fusing
Solution-cast is closed on polytetrafluoroethylene film, another composite membrane covering is then placed on hot press the heat under 80 DEG C and 10MPa pressure
Pressure certain time can form composite electrolyte membrane, and composite electrolyte can be formed after its is cold.
Embodiment 6
A kind of preparation method of richness lithium anti-perovskite oxide composite electrolyte, the richness lithium anti-perovskite oxide are compound
Electrolyte is prepared using melting pressure sintering, specifically includes the following steps:
By polymer (PEO), rich lithium anti-perovskite oxide (Li3OBr) with lithium salts (LiFSI) according to certain mass ratio
(7:3:1) is mixed into uniform compound, is then placed in crucible and is heated to 300 DEG C of heat preservation 5h, finally by the mixing of heat fusing
Another composite membrane covering is then placed on hot press the hot pressing one under 70 DEG C and 5MPa pressure on polytetrafluoroethylene film by solution-cast
Composite electrolyte membrane can be formed by fixing time, and composite electrolyte can be formed after its is cold.
Embodiment 7
A kind of preparation method of richness lithium anti-perovskite oxide composite electrolyte, the richness lithium anti-perovskite oxide are compound
Electrolyte is prepared using melting pressure sintering, specifically includes the following steps:
By polymer (PCL), rich lithium anti-perovskite oxide (Li3OCl) with lithium salts (LiTFSI) according to certain quality
It is mixed into uniform compound than (6:2:2), is then placed in crucible and is heated to 200 DEG C of heat preservation 2h, finally by the mixed of heat fusing
Solution-cast is closed on polytetrafluoroethylene film, another composite membrane covering is then placed on hot press the heat under 80 DEG C and 10MPa pressure
Pressure certain time can form composite electrolyte membrane, and composite electrolyte can be formed after its is cold.
Embodiment 8
A kind of preparation method of richness lithium anti-perovskite oxide composite electrolyte, the richness lithium anti-perovskite oxide are compound
Electrolyte is prepared using melting pressure sintering, specifically includes the following steps:
By polymer (PEO), rich lithium anti-perovskite oxide (Li3OBr) with lithium salts (LiFSI) according to certain mass ratio
(7:3:1) is mixed into uniform compound, is then placed in crucible and is heated to 300 DEG C of heat preservation 5h, finally by the mixing of heat fusing
Another composite membrane covering is then placed on hot press the hot pressing one under 70 DEG C and 5MPa pressure on polytetrafluoroethylene film by solution-cast
Composite electrolyte membrane can be formed by fixing time, and composite electrolyte can be formed after its is cold.
Embodiment 9
A kind of preparation method of richness lithium anti-perovskite oxide composite electrolyte, the richness lithium anti-perovskite oxide are compound
Electrolyte is prepared using melting pressure sintering, specifically includes the following steps:
By polymer (PCL), rich lithium anti-perovskite oxide (Li3OCl) with lithium salts (LiTFSI) according to certain quality
It is mixed into uniform compound than (6:2:2), is then placed in crucible and is heated to 200 DEG C of heat preservation 2h, finally by the mixed of heat fusing
Solution-cast is closed on polytetrafluoroethylene film, another composite membrane covering is then placed on hot press the heat under 80 DEG C and 10MPa pressure
Pressure 6h can form composite electrolyte membrane, and composite electrolyte can be formed after its is cold.
Embodiment 10
A kind of preparation method of richness lithium anti-perovskite oxide composite electrolyte, the richness lithium anti-perovskite oxide are compound
Electrolyte is prepared using melting pressure sintering, specifically includes the following steps:
By polymer (PEO), rich lithium anti-perovskite oxide (Li3OBr) with lithium salts (LiFSI) according to certain mass ratio
(7:3:1) is mixed into uniform compound, is then placed in crucible and is heated to 300 DEG C of heat preservation 5h, finally by the mixing of heat fusing
Another composite membrane covering is then placed on hot press the hot pressing 2h under 70 DEG C and 5MPa pressure on polytetrafluoroethylene film by solution-cast
Composite electrolyte membrane can be formed, composite electrolyte can be formed after its is cold.
Embodiment 11
A kind of preparation method of richness lithium anti-perovskite oxide composite electrolyte, the richness lithium anti-perovskite oxide are compound
Electrolyte is prepared using melting pressure sintering, specifically includes the following steps:
By polymer (PVDF-HFP), rich lithium anti-perovskite oxide (Li3OCl0.5Br0.5) with lithium salts (LiTFSI) according to
Certain mass ratio (7:2:1) is mixed into uniform compound, is then placed in crucible and is heated to 300 DEG C of heat preservation 5h, finally will
The mixed solution of heat fusing is cast on polytetrafluoroethylene film, then the covering of another composite membrane is placed on hot press at 100 DEG C and
Hot pressing can form composite electrolyte membrane for 24 hours under 10MPa pressure, and composite electrolyte can be formed after its is cold.
Embodiment 12
A kind of preparation method of richness lithium anti-perovskite oxide composite electrolyte, the richness lithium anti-perovskite oxide are compound
Electrolyte is prepared using melting pressure sintering, specifically includes the following steps:
By polymer (PVDF-HFP), rich lithium anti-perovskite oxide (Li3OCl0.3Br0.7) with lithium salts (LiFSI) according to
Certain mass ratio (6:2:2) is mixed into uniform compound, is then placed in crucible and is heated to 300 DEG C of heat preservation 5h, finally will
The mixed solution of heat fusing is cast on polytetrafluoroethylene film, then the covering of another composite membrane is placed on hot press at 100 DEG C and
Hot pressing 12h can form composite electrolyte membrane under 10MPa pressure, and composite electrolyte can be formed after its is cold.
Embodiment 13
A kind of preparation method of the all-solid-state battery comprising rich lithium anti-perovskite oxide composite electrolyte, it is described to include richness
The all-solid-state battery of lithium anti-perovskite oxide composite electrolyte is prepared using cast-in-place method, specifically includes the following steps:
The compound rich lithium anti-perovskite oxide composite electrolyte prepared is put into crucible and is heated to 300 DEG C and keeps its complete
Full-fusing forms the composite electrolyte membrane of 50 μ m-thicks at being cast in graphite (C) negative electrode tab after liquid, then sticks phosphorus in film
Sour iron lithium (LiFePO4) positive plate, rich lithium anti-perovskite battery is prepared to its cooling.
Embodiment 14
A kind of preparation method of the all-solid-state battery comprising rich lithium anti-perovskite oxide composite electrolyte, it is described to include richness
The all-solid-state battery of lithium anti-perovskite oxide composite electrolyte is prepared using cast-in-place method, specifically includes the following steps:
The compound rich lithium anti-perovskite oxide composite electrolyte prepared is put into crucible and is heated to 400 DEG C and keeps its complete
Full-fusing forms the composite electrolyte membrane of 80 μ m-thicks at being cast in graphite (C) negative electrode tab after liquid, then sticks cobalt in film
Sour lithium (LiCoO4) positive plate, rich lithium anti-perovskite battery is prepared to its cooling.
Embodiment 15
A kind of preparation method of the all-solid-state battery comprising rich lithium anti-perovskite oxide composite electrolyte, it is described to include richness
The all-solid-state battery of lithium anti-perovskite oxide composite electrolyte is prepared using cast-in-place method, specifically includes the following steps:
The compound rich lithium anti-perovskite oxide composite electrolyte prepared is put into crucible and is heated to 400 DEG C and keeps its complete
Full-fusing is at casting in cobalt acid lithium (LiCoO after liquid4) composite electrolyte membrane that 80 μ m-thicks are formed on positive plate, then in film
Stick lithium titanate (Li4Ti5O12) negative electrode tab, rich lithium anti-perovskite battery is prepared to its cooling.
Embodiment 16
A kind of preparation method of the all-solid-state battery comprising rich lithium anti-perovskite oxide composite electrolyte, it is described to include richness
The all-solid-state battery of lithium anti-perovskite oxide composite electrolyte is prepared using cast-in-place method, specifically includes the following steps:
LiFePO4 (LiFePO will be cast in after the compound rich lithium anti-perovskite oxide fusion prepared4) on positive plate
The composite electrolyte membrane for forming 60 μm, then sticks lithium titanate (Li in film4Ti5O12) negative electrode tab, it is prepared into its cooling
To rich lithium anti-perovskite battery.
Comparative example
Other solid lithium ion electrolyte without rich lithium anti-perovskite oxide in electrolyte on the market.
Selected by the composite electrolyte and comparative example being prepared using preparation method described in 1-12 of the embodiment of the present invention
All-solid-state battery is tested for the property and makes a concrete analysis of the thickness of its decomposition voltage, lithium ion conductivity and composite electrolyte, attached
Fig. 1 is the LSV curve of rich lithium anti-perovskite composite electrolyte provided in an embodiment of the present invention；Attached drawing 2 is that the embodiment of the present invention mentions
The EIS curve of the rich lithium anti-perovskite composite electrolyte supplied；Attached drawing 3 is that rich lithium anti-perovskite provided in an embodiment of the present invention is compound
The SEM photograph of the section thickness of electrolyte.
Data analysis result such as table 1:
Electrolyte that 1 present invention of table is prepared with
It can be obtained by table 1, utilize solution casting method described in the embodiment of the present invention or the melting any method system of pressure sintering
Standby obtained rich lithium anti-perovskite oxide electrolyte, the decomposition voltage of obtained rich lithium anti-perovskite oxide electrolyte are
4.0~5.0V, decomposition voltage window is wide, and obtained composite electrolyte electrochemical stability is high.Its obtained lithium ion conductivity
It is 10-6~10-3S cm-1Between, the conductivity of lithium ion is high, the lithium ion battery prepared using the composite electrolyte
It can be more excellent.Also, the composite electrolyte thickness is controllable, preparation-obtained electrolyte with a thickness of 50~500 μm, thickness
Controllably, battery can be made to give full play to its new energy.Its decomposition voltage of electrolyte described in comparative example is 4.2~4.5V, decomposition voltage
Window is significantly less than the rich lithium anti-perovskite oxide electrolyte that the present invention is prepared, therefore, the richness that the present invention is prepared
Lithium anti-perovskite oxide electrolyte electrochemical stability is higher.Secondly, the lithium ion conductivity of electrolyte described in comparative example
≤10-4S cm-1, conductivity is low, sufficiently affects the working performance of battery；In addition, comparative example preparation electrolyte with a thickness of
30~100 μm, thickness degree of controllability is smaller, is easy to influence battery performance.
In conclusion having the advantage that lithium ion conductance using composite electrolyte prepared by either present invention method
Rate height (10-6~10-3S cm-1)；Electrochemical stability is high, is 4~7V；Thickness is controllable, is 1 μm of -5cm；Good mechanical property；Electricity
Xie Zhiyu electrode wellability is good, and interface impedance is small, good cycling stability, and high rate performance is high；Preparation process is simple, at low cost.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. a kind of richness lithium anti-perovskite oxide composite electrolyte, which is characterized in that the richness lithium anti-perovskite oxide is compound
The material of electrolyte includes polymer, lithium salts and filler, and the filler is rich lithium anti-perovskite oxide.
2. richness lithium anti-perovskite oxide composite electrolyte according to claim 1, which is characterized in that the anti-calcium of the richness lithium
Titanium ore oxide structure formula general formula is Li3-xHxOA1-yBy, wherein A and B is halogens, 0≤x≤1,0≤y≤1.
3. according to claim 1 or 2 any rich lithium anti-perovskite oxide composite electrolytes, which is characterized in that described
Mass fraction of the rich lithium anti-perovskite oxide in the composite electrolyte is 1%~80%.
4. according to claim 1 or 2 any rich lithium anti-perovskite oxide composite electrolytes, which is characterized in that described
Rich lithium anti-perovskite oxide is selected from Li3OCl、Li2OHCl、Li3OBr、Li2OHBr、Li3OCl0.5Br0.5、Li3OCl0.7Br0.3、
Li3OCl0.3Br0.7、Li2OHCl0.9F0.1、Li3OCl0.8F0.2It is any.
5. according to claim 1 or 2 any rich lithium anti-perovskite oxide composite electrolytes, which is characterized in that described
Polymer is selected from polycaprolactone, polyethylene glycol oxide, polyacrylonitrile, polymethylacrylic acid, Kynoar, Kynoar-six
The one or more of fluoropropene, and/or；
The lithium salts is selected from lithium perchlorate, lithium hexafluoro phosphate, hexafluoroarsenate lithium, LiBF4, bis trifluoromethyl sulfimide
Lithium, double fluorine sulfimide lithiums, the one or more of trifluoromethyl sulfonic acid lithium, di-oxalate lithium borate, difluorine oxalic acid boracic acid lithium.
6. a kind of preparation method of richness lithium anti-perovskite oxide composite electrolyte, which is characterized in that using solution casting method or
Melt any one of pressure sintering preparation claim 1 to 5 rich lithium anti-perovskite oxide composite electrolyte.
7. the preparation method of richness lithium anti-perovskite oxide composite electrolyte according to claim 6, which is characterized in that adopt
The rich lithium anti-perovskite oxide composite electrolyte is prepared with solution casting method, comprising the following steps:
The polymer and the lithium salts are dissolved and obtain the first solution in organic solvent；
The rich lithium anti-perovskite oxide is added in first solution, is uniformly mixed and forms the second solution；
Second solution is cast on substrate, is dried in vacuo, obtains rich lithium anti-perovskite oxide composite electrolyte.
8. the preparation method of richness lithium anti-perovskite oxide composite electrolyte according to claim 6, which is characterized in that adopt
The rich lithium anti-perovskite oxide composite electrolyte is prepared with melting pressure sintering, comprising the following steps:
The rich lithium anti-perovskite oxide, the polymer are uniformly mixed with the lithium salts, heating melting forms electrolyte
Composite solution；
On the first substrate by electrolyte composite solution casting, deviate from the table of the first substrate in electrolyte composite solution
Face covers the second substrate, and hot pressing forms composite electrolyte membrane, is cooled to room temperature, obtains rich lithium anti-perovskite oxide combined electrolysis
Matter.
9. a kind of all-solid-state battery, by positive plate, negative electrode tab and the electrolysis between positive plate and negative electrode tab being oppositely arranged
Texture is at, which is characterized in that the electrolyte using the rich lithium anti-perovskite oxide combined electrolysis of any one of Claims 1 to 5
Matter or the electrolyte are the rich lithium anti-perovskite oxide compound electric that any one of claim 6~8 the method is prepared
Xie Zhi, and the rich lithium anti-perovskite oxide composite electrolyte with a thickness of 1 μm~5cm.
10. a kind of preparation method of all-solid-state battery, which comprises the following steps:
Rich lithium anti-perovskite oxide composite electrolyte is prepared according to any preparation method of the claims 6~8；
The rich lithium anti-perovskite oxide composite electrolyte heating melting is obtained into rich lithium anti-perovskite oxide composite electrolyte
Solution；
The rich lithium anti-perovskite oxide compound electrolyte solution is cast in the positive plate or negative electrode tab, is formed compound
Dielectric film；
The negative electrode tab being oppositely arranged or positive plate are sticked in the composite electrolyte membrane, is cooled to room temperature, the anti-calcium titanium of rich lithium is obtained
Mine battery.
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