CN107968219A - Inorganic solid electrolyte film and preparation method thereof and inorganic full-solid battery - Google Patents
Inorganic solid electrolyte film and preparation method thereof and inorganic full-solid battery Download PDFInfo
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- CN107968219A CN107968219A CN201610911598.9A CN201610911598A CN107968219A CN 107968219 A CN107968219 A CN 107968219A CN 201610911598 A CN201610911598 A CN 201610911598A CN 107968219 A CN107968219 A CN 107968219A
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention provides a kind of inorganic solid electrolyte film and preparation method thereof and inorganic full-solid battery.The inorganic solid electrolyte film includes polymeric matrix and inorganic electrolyte particle.The inorganic electrolyte particle forms individual particle dispersion layer and is scattered in the polymeric matrix, and the head of the inorganic electrolyte particle and afterbody are exposed independent from the polymeric matrix.The inorganic electrolyte particle includes sulphur system solid electrolyte.After the inorganic solid electrolyte film of the present invention is applied in inorganic full-solid battery, the energy density of inorganic full-solid battery can be significantly improved and substantially improve cycle performance.
Description
Technical field
The present invention relates to battery technology field, and in particular to a kind of inorganic solid electrolyte film and preparation method thereof and nothing
Machine all-solid-state battery.
Background technology
With the development of lithium ion battery technology, all-solid-state battery is increasingly subject to people to pay close attention to.Wherein, it is organic all solid state
For battery (or polymer all-solid-state battery) due to being limited be subject to operating temperature and electrolytic conductivity, progress is slower；And
The operating temperature range of inorganic full-solid battery is wide, and with the development of sulphur system solid electrolyte, electrical conductivity has not been limitation nothing
The principal element of machine solid state battery development, most of inorganic solid electrolyte layers use compression molding or coating in existing process
Method, but due to the characteristic of inorganic solid electrolyte granular powder, thickness and machinability are all influence its application unfavorable
Factor, since the Li dendrite that intergranular space is grown causes positive and negative anodes short circuit problem very common especially during later cycles.
For this problem, substantial amounts of researcher works in terms of organo-mineral complexing dielectric substrate, but same with this
When can cause the reduction of all-solid-state battery whole conductivity, and later stage short circuit problem as caused by Li dendrite is not changed greatly very much
It is kind.
The content of the invention
In view of problem present in background technology, it is an object of the invention to provide a kind of inorganic solid electrolyte film and
Its preparation method and inorganic full-solid battery, after the inorganic solid electrolyte film is applied in inorganic full-solid battery,
It is remarkably improved the energy density of inorganic full-solid battery and substantially improves cycle performance.
In order to achieve the above object, in the first aspect of the present invention, the present invention provides a kind of inorganic solid electrolyte is thin
Film, it includes polymeric matrix and inorganic electrolyte particle.The inorganic electrolyte particle forms individual particle dispersion layer and divides
Dissipate in the polymeric matrix, and the head of the inorganic electrolyte particle and afterbody are exposed independent from the polymeric matrix.Institute
Stating inorganic electrolyte particle includes sulphur system solid electrolyte.
In the second aspect of the present invention, the present invention provides a kind of preparation method of inorganic solid electrolyte film, it is used for
Prepare the inorganic solid electrolyte film described in first aspect present invention, including step：(1) polymer and organic solvent are mixed
Polymer solution is made into, polymer solution is coated on substrate surface；(2) inorganic electrolyte particle is disperseed individual particle point is made
Layer is dissipated, when the organic solvent in the polymer solution of substrate surface does not volatilize completely, by substrate coated with polymer solution
Simultaneously it is pressed against on the granuloplastic individual particle dispersion layer of inorganic electrolyte；(3) substrate is overturn, makes to be coated with polymer solution
One side upward, continue using step (1) method several times coated polymer solution until carrying out hot place to polymer solution
The thickness of the polymeric matrix obtained after reason disperses the thickness for the individual particle dispersion layer to be formed not less than inorganic electrolyte particle；
(4) removal substrate and the method by etching are exposed independent from the head of the inorganic electrolyte particle in individual particle dispersion layer and afterbody
In polymeric matrix, that is, obtain inorganic solid electrolyte film.
In the third aspect of the present invention, the present invention provides a kind of inorganic full-solid battery, it includes first party of the present invention
Inorganic solid electrolyte film described in face.
Relative to the prior art, beneficial effects of the present invention are：
After the inorganic solid electrolyte film of the present invention is applied in inorganic full-solid battery, it can significantly improve inorganic
The energy density of all-solid-state battery simultaneously substantially improves cycle performance.
Brief description of the drawings
Fig. 1 is the schematic cross-section of the inorganic solid electrolyte film of the present invention；
Fig. 2 is the AC impedance spectroscopy of comparative example 1 and embodiment 5；
Fig. 3 is the cycle performance test chart of comparative example 2 and embodiment 4.
Embodiment
The following detailed description of inorganic solid electrolyte film according to the present invention and preparation method thereof and inorganic full-solid electricity
Pond.
Illustrate inorganic solid electrolyte film according to a first aspect of the present invention first.
With reference to Fig. 1, inorganic solid electrolyte film according to a first aspect of the present invention includes polymeric matrix and inorganic
Electrolyte granular.The inorganic electrolyte particle forms individual particle dispersion layer and is scattered in the polymeric matrix, and the nothing
The head of machine electrolyte granular and afterbody are exposed independent from the polymeric matrix.The inorganic electrolyte particle includes sulphur system solid-state
Electrolyte.
In the inorganic solid electrolyte film described according to a first aspect of the present invention, the inorganic solid electrolyte film
Electrical conductivity and sulphur system solid electrolyte electrical conductivity in the same order of magnitude.
In the inorganic solid electrolyte film described according to a first aspect of the present invention, the electrical conductivity of sulphur system solid electrolyte
Height, the electrical conductivity of the inorganic solid electrolyte film of preparation with its in the same order of magnitude, so as to improve the energy density of battery.
In addition, with reference to Fig. 1, the head of each inorganic electrolyte particle and afterbody are exposed independent from can only in the polymeric matrix, lithium ion
Conducted in each inorganic electrolyte particle in individual particle dispersion layer, mechanical stress and the polymerization of individual particle can be efficiently used
The characteristic that thing matrix insulate ion suppresses the pore development of Li dendrite between particles, avoids causing short circuit, so that significantly
Improve the cycle performance of battery.
In the inorganic solid electrolyte film described according to a first aspect of the present invention, sulphur system solid electrolyte is selected from
Li10GeP2S12、Li10SnP2S12、Li10SiP2S12、Li2S-P2S5-LiI、Li2S-P2S5、B2S3-Li2S-LiI、Li2S-SiS2-
LiPO4、Li2S-SiS2-Li4SiO4、Li3.25Ge0.25P0.24S4、Li10GeP2S11In one or more.Specifically, Li2S-P2S5
Can be Li7P3S11Or Li3.25P0.95S4。
In the inorganic solid electrolyte film described according to a first aspect of the present invention, the polymeric matrix is selected from and does not lead
Electronics and ion and the not polymer with the inorganic electrolyte particle reaction.Specifically, the polymeric matrix may be selected from benzene
Ethylene-butadiene-styrene block copolymer (SBS), nitrile rubber (NBR), Kynoar (PVDF), vinylidene-six
One or more in fluoropropene copolymer.
In the inorganic solid electrolyte film described according to a first aspect of the present invention, the electricity of sulphur system solid electrolyte
Conductance can be more than or equal to 10-4S/cm.Preferably, the electrical conductivity of sulphur system solid electrolyte can be more than or equal to 10-3S/cm。
In the inorganic solid electrolyte film described according to a first aspect of the present invention, of sulphur system solid electrolyte
Granularity is 10 μm~100 μm.Preferably, the granularity of sulphur system solid electrolyte is 40 μm~80 μm.
In the inorganic solid electrolyte film described according to a first aspect of the present invention, the inorganic solid electrolyte film
Thickness be less than or equal to 100 μm, the thickness of inorganic full-solid battery is so advantageously reduced, so that the energy for improving battery is close
Degree.
Secondly the preparation method of the inorganic solid electrolyte film of explanation according to a second aspect of the present invention.
The preparation method of inorganic solid electrolyte film according to a second aspect of the present invention, is used to prepare first party of the present invention
Inorganic solid electrolyte film described in face, including step：(1) polymer and organic solvent are mixed and are made into polymer solution,
Polymer solution is coated on substrate surface；(2) inorganic electrolyte particle is disperseed individual particle dispersion layer is made, in substrate surface
Polymer solution in organic solvent when not volatilizing completely, one side of the substrate coated with polymer solution is pressed against no electromechanics
Solve on the granuloplastic individual particle dispersion layer of matter；(3) substrate is overturn, makes the one side coated with polymer solution upward, continued
Using step (1) method several times coated polymer solution until the thickness of polymeric matrix obtained after heat treatment is not less than
Inorganic electrolyte particle disperses the thickness for the individual particle dispersion layer to be formed；(4) remove substrate and make single by the method for etching
The head of inorganic electrolyte particle in grain dispersion layer and afterbody are exposed independent from polymeric matrix, that is, obtaining inorganic solid electrolyte
Film.
In the preparation method of the inorganic solid electrolyte film described according to a second aspect of the present invention, in step (1),
The substrate may be selected from silicon chip, carborundum.
In the preparation method of the inorganic solid electrolyte film described according to a second aspect of the present invention, in step (1),
Organic solvent is selected from not with the material of sulphur system solid state electrolysis qualitative response or does not reduce the order of magnitude of sulphur system solid electrolyte electrical conductivity
Material.Specifically, organic solvent may be selected from nonpolar or low pole Long carbon chain alkanes, amine, long-chain alcohols, ethers,
The organic solvents such as esters.Preferably, organic solvent is selected from dimethylbenzene, toluene, heptane, triethylamine, cyclopentyl methyl ether, butyric acid fourth
One or more in ester, 2,6- dimethyl enanthol.
In the preparation method of the inorganic solid electrolyte film described according to a second aspect of the present invention, in step (1),
The weight percent concentration of polymer solution is more than 0 and less than or equal to 20%.Preferably, the percentage by weight of polymer solution is dense
Spend for 5%~10%.
In the preparation method of the inorganic solid electrolyte film described according to a second aspect of the present invention, in step (1),
The coating method of polymer solution is preferably spin coating, and the thicknesses of layers of inorganic solid electrolyte film can be made by the way of spin coating
Uniformity higher.
In the preparation method of the inorganic solid electrolyte film described according to a second aspect of the present invention, in step (1),
The coating thickness of polymer solution is smaller than being equal to 20 μm, preferably smaller than equal to 10 μm.It is further preferred that heat is carried out after coating
Handle to discharge the residual gas in coat.
In the preparation method of the inorganic solid electrolyte film described according to a second aspect of the present invention, in step (1),
The coating processing of polymer solution can be carried out several times, and the thickness coated every time is smaller than being equal to 20 μm, is preferably smaller than equal to
10 μm, it is further preferred that being heat-treated every time after coating to discharge the residual gas in coat.Repeatedly coat and each
Carry out being heat-treated the stomata quantity that can effectively reduce in coating after coating, improve the uniformity of inorganic solid electrolyte film, from
And improve transport properties of the inorganic solid electrolyte film to lithium ion, improve the cycle performance of inorganic full-solid battery.
In the preparation method of the inorganic solid electrolyte film described according to a second aspect of the present invention, in step (3),
During continuing coated polymer solution several times, the thickness coated every time is smaller than being equal to 20 μm, preferably smaller than equal to 10 μ
M, it is further preferred that being heat-treated every time after coating to discharge the residual gas in coat.Repeatedly coating and every time painting
Carry out being heat-treated the stomata quantity that can effectively reduce in coating after covering, improve the uniformity of inorganic solid electrolyte film, so that
Improve transport properties of the inorganic solid electrolyte film to lithium ion, improve the cycle performance of inorganic full-solid battery.
, every time can after coating in the preparation method of the inorganic solid electrolyte film described according to a second aspect of the present invention
The residual gas in coat is discharged by the way of heat treatment, wherein heat treatment temperature can be 50 DEG C~200 DEG C, be preferably 80
DEG C~150 DEG C；Heat treatment time may be less than 5h, be preferably 10min~30min.The purpose of heat treatment is to make polymeric matrix
Melting but Undec state, the convenient multiple coating subsequently carried out is presented, and is reached by heat treatment and reduces inorganic solid-state electricity
The purpose of stomata quantity in matter film is solved, so as to improve the cycle performance of inorganic full-solid battery.
In the preparation method of the inorganic solid electrolyte film described according to a second aspect of the present invention, in step (2),
Powder similar in granularity can be filtered out by vibrating sub-sieve, and sulphur system solid electrolyte is disperseed individual particle dispersion layer is made.
In the preparation method of the inorganic solid electrolyte film described according to a second aspect of the present invention, in step (3),
The difference of the thickness of polymeric matrix and the thickness of individual particle dispersion layer is more than or equal to 0 and less than or equal to 10 μm.Preferably, polymer
The difference of the thickness of matrix and the thickness of individual particle dispersion layer is more than or equal to 0 and less than or equal to 0.5 μm.
In the preparation method of the inorganic solid electrolyte film described according to a second aspect of the present invention, in step (4),
It can make head and the tail of the inorganic electrolyte particle in individual particle dispersion layer using the method that ion beam etching or ultraviolet light etch
Portion is exposed independent from polymeric matrix.
In the preparation method of the inorganic solid electrolyte film described according to a second aspect of the present invention, step (1)~(4)
Operated under inert atmosphere protection.Preferably, inert gas is argon gas.
Illustrate inorganic full-solid battery according to a third aspect of the present invention again.
Inorganic full-solid battery according to a third aspect of the present invention includes described inorganic solid according to a first aspect of the present invention
State electrolytic thin-membrane.
In the inorganic full-solid battery described according to a third aspect of the present invention, the inorganic full-solid battery further includes negative
Pole piece and positive plate.There is the inorganic solid electrolyte film at interval between adjacent positive piece and negative plate.
In the inorganic full-solid battery described according to a third aspect of the present invention, the positive plate include plus plate current-collecting body with
And it is arranged at the positive electrode material layer on plus plate current-collecting body.The positive electrode material layer includes positive electrode and electrolyte.It is described just
Pole material layer is by obtaining the mixture of positive electrode and electrolyte is compressing.The positive electrode may be selected from conventional cathode
Material such as LiCoO2、LiMnO2、LiNiO2、LiVO2、LiNixCoyMn1-x-yO2(0 ＜ x ＜, 1,0 ＜ y ＜ 1, and 0 ＜ x+y ＜
1)、LiMn2O4、Li(Ni0.5Mn1.5)O4、LiNi0.8Co0.15Al0.05O2、LiFePO4、LiMnPO4And its one kind in modified material
It is or several.Wherein, the addition of electrolyte establishes ionic conduction network in positive electrode material layer, enhances leading for positive electrode material layer
It is ionic.In positive electrode material layer, the percentage by weight of positive electrode and electrolyte is 6:4~8:2.Preferably, the electrolysis
Matter can be sulphur system solid electrolyte.
In the inorganic full-solid battery described according to a third aspect of the present invention, the negative plate may include negative current collector
And it is arranged at the negative electrode material layer on negative current collector.The negative electrode material layer includes negative material and electrolyte.It is described
Negative electrode material layer can be by obtaining the mixture of negative material and electrolyte is compressing.The negative material may be selected from stone
One or more in ink, silicon, lithium titanate.Wherein, the addition of electrolyte establishes ionic conduction network in negative electrode material layer,
It is ionic to enhance leading for negative electrode material layer.In negative electrode material layer, the percentage by weight of negative material and electrolyte is 4:6~
7:3.Preferably, electrolyte can be sulphur system solid electrolyte.
In the inorganic full-solid battery described according to a third aspect of the present invention, the negative plate can also directly use metal
Pole piece made of lithium and its alloy.
With reference to embodiment, the application is expanded on further.It is to be understood that these embodiments be merely to illustrate the application without
For limiting scope of the present application.
In the examples below, used material, reagent and instrument be not as having specified otherwise, commercially
Purchase obtains.
Embodiment 1
(1) preparation of inorganic solid electrolyte film
NBR is dissolved in be made into dimethylbenzene concentration be 8wt% polymer solution, use spin coating mode (rotating speed for
3000rpm), polymer solution is coated in substrate surface, coating thickness is 10 μm.
Using electrical conductivity as 2.2 × 10-3S/cm, the Li that granularity is 40 μm~50 μm7P3S11As inorganic electrolyte particle,
Method by vibrating sub-sieve is made into individual particle dispersion layer.
When dimethylbenzene in the polymer solution of substrate surface does not volatilize completely, by substrate coated with polymer solution
Simultaneously it is pressed against on individual particle dispersion layer, is heat-treated 20min at 80 DEG C afterwards.
Substrate is overturn, makes the one side coated with polymer solution upward, continues to coat several times using the method for spin coating
Polymer solution, wherein, each coating thickness is not more than 10 μm, and 80 DEG C of heat treatment 20min after coating every time, until heat treatment
After the obtained thickness of polymeric matrix be not less than the thickness of individual particle dispersion layer, it is less than or equal to 10 μm beyond height.
Remove substrate and use the method for ion beam etching to make the head of the inorganic electrolyte particle in individual particle dispersion layer
It is exposed independent from afterbody in polymeric matrix, finally obtains the inorganic solid electrolyte film of about 50 μm of thickness.
(2) preparation of inorganic full-solid battery
Positive electrode material layer is by by the mixture of positive electrode and electrolyte (weight ratio 7:3) compacting layered obtains.
Wherein, positive electrode uses Li using the cobalt acid lithium for coating lithium niobate, electrolyte7P3S11.Plus plate current-collecting body uses aluminium foil.
Negative plate is used as using metal lithium sheet.
Positive electrode material layer, inorganic solid electrolyte film and negative plate are prepared into Sanming City by the way of pressure forming
The battery layers of type are controlled, then enclosing plus plate current-collecting body in positive terminal is assembled into inorganic full-solid battery.
Aforesaid operations process carries out in the glove box of nitrogen atmosphere.
Cycle performance test equipment is blue electric battery test system, and charging and discharging currents are 0.1C in test process, charging
Blanking voltage is 4.2V, discharge cut-off voltage 3.0V.
Embodiment 2
(1) preparation of inorganic solid electrolyte film
NBR is dissolved in be made into dimethylbenzene concentration be 8wt% polymer solution, use spin coating mode (rotating speed for
3000rpm), polymer solution is coated in substrate surface, coating thickness is 10 μm.
Using electrical conductivity as 2.2 × 10-3S/cm, the Li that granularity is 20 μm~30 μm7P3S11As inorganic electrolyte particle,
Method by vibrating sub-sieve is made into individual particle dispersion layer.
When dimethylbenzene in the polymer solution of substrate surface does not volatilize completely, by substrate coated with polymer solution
Simultaneously it is pressed against on individual particle dispersion layer, is heat-treated 20min at 80 DEG C afterwards.
Substrate is overturn, makes the one side coated with polymer solution upward, continues to coat several times using the method for spin coating
Polymer solution, wherein, each coating thickness is not more than 10 μm, and 80 DEG C of heat treatment 20min after coating every time, until heat treatment
After the obtained thickness of polymeric matrix be not less than the thickness of individual particle dispersion layer, it is less than or equal to 10 μm beyond height.
Remove substrate and use the method for ion beam etching to make the head of the inorganic electrolyte particle in individual particle dispersion layer
It is exposed independent from afterbody in polymeric matrix, finally obtains the inorganic solid electrolyte film of about 20 μm of thickness.
(2) preparation of inorganic full-solid battery
Positive electrode material layer is by by the mixture of positive electrode and electrolyte (weight ratio 7:3) compacting layered obtains.
Wherein, positive electrode uses Li using the cobalt acid lithium for coating lithium niobate, electrolyte7P3S11.Plus plate current-collecting body uses aluminium foil.
Negative plate is used as using metal lithium sheet.
Positive electrode material layer, inorganic solid electrolyte film and negative plate are prepared into Sanming City by the way of pressure forming
The battery layers of type are controlled, then enclosing plus plate current-collecting body in positive terminal is assembled into inorganic full-solid battery.
Aforesaid operations process carries out in the glove box of nitrogen atmosphere.
Cycle performance test equipment is blue electric battery test system, and charging and discharging currents are 0.1C in test process, charging
Blanking voltage is 4.2V, discharge cut-off voltage 3.0V.
Embodiment 3
(1) preparation of inorganic solid electrolyte film
NBR is dissolved in be made into dimethylbenzene concentration be 8wt% polymer solution, use spin coating mode (rotating speed for
3000rpm), polymer solution is coated in substrate surface, coating thickness is 10 μm.
Using electrical conductivity as 2.2 × 10-3S/cm, the Li that granularity is 90~100 μm7P3S11As inorganic electrolyte particle,
Method by vibrating sub-sieve is made into individual particle dispersion layer.
When dimethylbenzene in the polymer solution of substrate surface does not volatilize completely, by substrate coated with polymer solution
Simultaneously it is pressed against on individual particle dispersion layer, is heat-treated 20min at 80 DEG C afterwards.
Substrate is overturn, makes the one side coated with polymer solution upward, continues to coat several times using the method for spin coating
Polymer solution, wherein, each coating thickness is not more than 10 μm, and 80 DEG C of heat treatment 20min after coating every time, until heat treatment
After the obtained thickness of polymeric matrix be not less than the thickness of individual particle dispersion layer, it is less than or equal to 10 μm beyond height.
Remove substrate and use the method for ion beam etching to make the head of the inorganic electrolyte particle in individual particle dispersion layer
It is exposed independent from afterbody in polymeric matrix, finally obtains the inorganic solid electrolyte film of about 100 μm of thickness.
(2) preparation of inorganic full-solid battery
Positive electrode material layer is by by the mixture of positive electrode and electrolyte (weight ratio 7:3) compacting layered obtains.
Wherein, positive electrode uses Li using the cobalt acid lithium for coating lithium niobate, electrolyte7P3S11.Plus plate current-collecting body uses aluminium foil.
Negative plate is used as using metal lithium sheet.
Positive electrode material layer, inorganic solid electrolyte film and negative plate are prepared into Sanming City by the way of pressure forming
The battery layers of type are controlled, then enclosing plus plate current-collecting body in positive terminal is assembled into inorganic full-solid battery.
Aforesaid operations process carries out in the glove box of nitrogen atmosphere.
Cycle performance test equipment is blue electric battery test system, and charging and discharging currents are 0.1C in test process, charging
Blanking voltage is 4.2V, discharge cut-off voltage 3.0V.
Embodiment 4
(1) preparation of inorganic solid electrolyte film
SBS is dissolved in be made into heptane concentration be 5wt% polymer solution, use spin coating mode (rotating speed for
3000rpm), polymer solution is coated in substrate surface, coating thickness is 10 μm.
Using electrical conductivity as 5 × 10-3S/cm, the Li that granularity is 70 μm~80 μm10GeP2S12As inorganic electrolyte
Grain, the method by vibrating sub-sieve are made into individual particle dispersion layer.
When heptane in the polymer solution of substrate surface does not volatilize completely, substrate is coated with the one of polymer solution
Face is pressed against on individual particle dispersion layer, is heat-treated 20min at 80 DEG C afterwards.
Substrate is overturn, makes the one side coated with polymer solution upward, continues to coat several times using the method for spin coating
Polymer solution, wherein, each coating thickness is not more than 10 μm, and 80 DEG C of heat treatment 20min after coating every time, until heat treatment
After the obtained thickness of polymeric matrix be not less than the thickness of individual particle dispersion layer, it is less than or equal to 10 μm beyond height.
Remove substrate and use the method for ion beam etching to make the head of the inorganic electrolyte particle in individual particle dispersion layer
It is exposed independent from afterbody in polymeric matrix, finally obtains the inorganic solid electrolyte film of about 80 μm of thickness.
(2) preparation of inorganic full-solid battery
Positive electrode material layer is by by the mixture of positive electrode and electrolyte (weight ratio 7:3) compacting layered obtains.
Wherein, positive electrode uses Li using the cobalt acid lithium for coating lithium niobate, electrolyte10GeP2S12.Plus plate current-collecting body uses aluminium foil.
Negative plate is used as using lithium indium alloy.
Positive electrode material layer, inorganic solid electrolyte film and negative plate are prepared into Sanming City by the way of pressure forming
The battery layers of type are controlled, then enclosing plus plate current-collecting body in positive terminal is assembled into inorganic full-solid battery.
Aforesaid operations process carries out in the glove box of nitrogen atmosphere.
Cycle performance test equipment is blue electric battery test system, and charging and discharging currents are 0.1C in test process, charging
Blanking voltage is 3.58V, discharge cut-off voltage 2.0V.
Embodiment 5
(1) preparation of inorganic solid electrolyte film
By VDF and HFP according to mass ratio 9:The polymer for being made into that concentration is 5wt% in butyl butyrate is dissolved in after 1 mixing
Solution, uses the mode (rotating speed 3000rpm) of spin coating, polymer solution is coated in substrate surface, coating thickness is 10 μm.
Using electrical conductivity as 3.48 × 10-3The 70Li of S/cm, 40 μm~50 μm of granularity2S-29P2S5- LiI is as no electromechanics
Matter particle is solved, the method by vibrating sub-sieve is made into individual particle dispersion layer.
When butyl butyrate in the polymer solution of substrate surface does not volatilize completely, substrate is coated with polymer solution
One side be pressed against on individual particle dispersion layer, afterwards 80 DEG C be heat-treated 20min.
Substrate is overturn, makes the one side coated with polymer solution upward, continues to coat several times using the method for spin coating
Polymer solution, wherein, each coating thickness is not more than 10 μm, and 80 DEG C of heat treatment 20min after coating every time, until heat treatment
After the obtained thickness of polymeric matrix be not less than the thickness of individual particle dispersion layer, it is less than or equal to 10 μm beyond height.
Remove substrate and make the head of the inorganic electrolyte particle in individual particle dispersion layer using the method that ultraviolet light etches
It is exposed independent from afterbody in polymeric matrix, finally obtains the inorganic solid electrolyte film that thickness is about 50 μm.
(2) preparation of inorganic full-solid battery
Positive electrode material layer is by by the mixture of positive electrode and electrolyte (weight ratio 7:3) compacting layered obtains.
Wherein, positive electrode uses 70Li using the cobalt acid lithium for coating lithium niobate, electrolyte2S-29P2S5-LiI.Plus plate current-collecting body uses
Aluminium foil.
Negative electrode material layer is by by the mixture of negative material and electrolyte (weight ratio 5:5) compacting layered obtains.
Wherein, negative material uses graphite, and electrolyte uses 70Li2S-29P2S5-LiI.Negative current collector uses copper foil.
Positive electrode material layer, inorganic solid electrolyte film and negative electrode material layer are prepared into by the way of pressure forming
The battery layers of sandwich type, then enclose collector in positive and negative end and are assembled into inorganic full-solid battery respectively.
Aforesaid operations process carries out in the glove box of nitrogen atmosphere.
Cycle performance test equipment is blue electric battery test system, and charging and discharging currents are 0.1C in test process, charging
Blanking voltage is 4.2V, discharge cut-off voltage 3.0V.
Comparative example 1
The preparation of inorganic full-solid battery is with embodiment 3, and difference lies in inorganic solid electrolyte film is free of polymer matrix
Body sulf onyl system electrolyte granular, and obtained using compression molding, the thickness of inorganic solid electrolyte film is about 600 μm.
Comparative example 2
The preparation of inorganic full-solid battery is with embodiment 2, and difference lies in inorganic solid electrolyte film is free of polymer matrix
Body sulf onyl system electrolyte granular, and obtained using compression molding, the thickness of inorganic solid electrolyte film is about 600 μm.
The test result of table 1 embodiment 1-5 and comparative example 1-2
Table 1 for embodiment 1-5 and comparative example 1-2 electrical conductivity and capacity attenuation to 80% cycle-index measurement result,
Its conductance of the film of solid inorganic solid electrolyte preparation of variable grain degree is can be seen that from the conductivity data of embodiment 1-3
Rate difference is little, 10-3The order of magnitude；From loop-around data it can be seen that solid electrolyte particle system of the granularity at 40~50 μm
Standby film loop-around data is optimal, this is because using behaviour of the granularity for 20 μm or so of solid electrolyte particle preparation film
Make that difficulty is bigger, the homogeneity and integrality of film are poor, therefore poor circulation, and granularity is 100 μm or so
The film that solid electrolyte particle finally obtains is thicker, causes the dynamic performance of inorganic full-solid battery poor, still
Influenced in the case of small rate charge-discharge less, to sum up the granularity optimized scope for the solid electrolyte particle that we choose exists
40-80μm。
Fig. 2 is the AC impedance spectroscopy of comparative example 1 and embodiment 5, wherein, the electrical conductivity of inorganic solid electrolyte film is adopted
Electrode is done with lithium metal, test equipment is defeated power forceful electric power chem workstation 1470E, frequency range 0.1-1000000Hz, and disturbance is electric
Press as 100mV.As can be seen from Figure 2, the impedance of the inorganic solid electrolyte film of embodiment 5 is 4.8 Ω, comparative example 1 it is inorganic solid
The impedance of state electrolytic thin-membrane is 22.7 Ω.The net sectional area of embodiment 5 and comparative example 1 is all 0.785cm2, therefore by electricity
The electrical conductivity that embodiment 5 is calculated in conductance formula is 1.49 × 10-3S/cm, the electrical conductivity of comparative example 1 is 3.48 × 10-3S/
cm.It can thus be concluded that going out, the electrical conductivity of inorganic solid electrolyte film of the invention is with using sulphur system electrolyte granular compression molding
Inorganic solid electrolyte film electrical conductivity it is lower slightly, but without the change on the order of magnitude.
Fig. 3 is the cycle performance test chart of comparative example 2 and embodiment 4.As can be seen from Figure 3, the electric discharge specific volume first of comparative example 2
Measure as 128.7mAh/g, capacity retention ratio is reduced to less than 80% after 50 circulations, then due to there is Li dendrite, causes electricity
Micro-short circuit inside pond, capacity retention ratio drastically decline.The first discharge specific capacity of embodiment 4 is 125.2mAh/g, than comparative example 2
It is slightly lower, this is because contain polymeric matrix in the inorganic solid electrolyte film of embodiment 4, therefore impedance is big compared with comparative example 2
Caused by.The capacity retention ratio after about 90 circulations of embodiment 4 is reduced to less than 80%, but as the further of circulation carries out,
The phenomenon that the specific discharge capacity of embodiment 4 does not decline drastically.The volume energy density ratio of the inorganic full-solid battery of the present invention
Volume energy density using the inorganic full-solid battery of the inorganic solid electrolyte film by powder compression molding is high, and this hair
Bright inorganic full-solid battery can reduce the generation of Li dendrite, therefore the cycle performance of inorganic full-solid battery is obviously improved.
The above is in conjunction with specific embodiments to the detailed description of the invention done, it is not limited to these explanations.To this
The technical staff for inventing the field should be in the protection of the present invention based on some modifications and changes that thinking of the present invention is done
In the range of.
Claims (10)
1. a kind of inorganic solid electrolyte film, including：
Polymeric matrix；And
Inorganic electrolyte particle；
It is characterized in that,
The inorganic electrolyte particle forms individual particle dispersion layer and is scattered in the polymeric matrix, and the inorganic electrolyte
The head of particle and afterbody are exposed independent from the polymeric matrix；
The inorganic electrolyte particle includes sulphur system solid electrolyte.
2. inorganic solid electrolyte film according to claim 1, it is characterised in that sulphur system solid electrolyte is selected from
Li10GeP2S12、Li10SnP2S12、Li10SiP2S12、Li2S-P2S5-LiI、Li2S-P2S5、B2S3-Li2S-LiI、Li2S-SiS2-
LiPO4、Li2S-SiS2-Li4SiO4、Li3.25Ge0.25P0.24S4、Li10GeP2S11In one or more.
3. inorganic solid electrolyte film according to claim 1, it is characterised in that the polymeric matrix is selected from and does not lead
Electronics and ion and the not polymer with the inorganic electrolyte particle reaction.
4. inorganic solid electrolyte film according to claim 3, it is characterised in that the polymeric matrix is selected from benzene second
One in alkene-butadiene-styrene block copolymer, nitrile rubber, Kynoar, vinylidene fluoride-hexafluoropropylene copolymer
Kind is several.
5. inorganic solid electrolyte film according to claim 1, it is characterised in that the electricity of sulphur system solid electrolyte
Conductance is more than or equal to 10-4S/cm, preferably greater than equal to 10-3S/cm。
6. inorganic solid electrolyte film according to claim 1, it is characterised in that of sulphur system solid electrolyte
Granularity is 10 μm~100 μm, is preferably 40 μm~80 μm.
7. inorganic solid electrolyte film according to claim 1, it is characterised in that the inorganic solid electrolyte film
Thickness be less than or equal to 100 μm.
8. a kind of preparation method of inorganic solid electrolyte film, is used to prepare inorganic any one of claim 1-7
Solid electrolyte film, it is characterised in that including step：
(1) polymer and organic solvent are mixed and is made into polymer solution, polymer solution is coated on substrate surface；
(2) inorganic electrolyte particle is disperseed individual particle dispersion layer is made, it is organic molten in the polymer solution of substrate surface
When agent is not volatilized completely, one side of the substrate coated with polymer solution is pressed against inorganic electrolyte granuloplastic individual particle point
Dissipate on layer；
(3) substrate is overturn, makes the one side coated with polymer solution upward, continue to apply several times using the method for step (1)
The thickness of the polymeric matrix obtained after covering polymer solution until being heat-treated to polymer solution is not less than inorganic electrolyte
Matter particle disperses the thickness for the individual particle dispersion layer to be formed；
(4) removal substrate and the method by etching make the head of the inorganic electrolyte particle in individual particle dispersion layer and afterbody equal
Polymeric matrix is exposed to, that is, obtains inorganic solid electrolyte film.
9. the preparation method of inorganic solid electrolyte film according to claim 8, it is characterised in that in step (3),
The difference of the thickness of polymeric matrix and the thickness of individual particle dispersion layer is more than or equal to 0 and less than or equal to 10 μm, it is preferable that polymer
The difference of the thickness of matrix and the thickness of individual particle dispersion layer is more than or equal to 0 and less than or equal to 0.5 μm.
10. a kind of inorganic full-solid battery, it is characterised in that including inorganic solid according to any one of claim 1-7
State electrolytic thin-membrane.
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Application publication date: 20180427 |