CN104103873B - Solid electrolyte film, and preparation method and application of solid electrolyte film - Google Patents
Solid electrolyte film, and preparation method and application of solid electrolyte film Download PDFInfo
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- CN104103873B CN104103873B CN201410290828.5A CN201410290828A CN104103873B CN 104103873 B CN104103873 B CN 104103873B CN 201410290828 A CN201410290828 A CN 201410290828A CN 104103873 B CN104103873 B CN 104103873B
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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
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell 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
- H01M2300/0071—Oxides
Abstract
The invention discloses a solid electrolyte film, and a preparation method and an application of the solid electrolyte film. The solid electrolyte film comprises a solid electrolyte layer and a porous ceramic layer, wherein the thickness of the solid electrolyte layer is 0.5-10 micrometers; the thickness of the porous ceramic layer is 100-300 micrometers; and the solid electrolyte layer uniformly covers the porous ceramic layer. The preparation method of the solid electrolyte film comprises the following steps of (1) preparing a solid electrolyte precursor: sintering raw material powder at 500-700 DEG C, (2) preparing a solid electrolyte target material: adding the powder to a binding agent, pressing the binding agent into sheets and sintering, and (3) applying the solid electrolyte film on a porous ceramic substrate: uniformly applying the solid electrolyte film on porous ceramic by a magnetron sputtering method. The solid electrolyte film has good ionic conduction properties and mechanical properties, is applied to preparation of a lithium air battery, and is low in internal resistance and good in electrical performance. The method is simple in technology and low in cost.
Description
Technical field
The invention belongs to solid electrolyte field, more particularly, to a kind of solid electrolyte membrane and its application.
Background technology
Along with the fast development of electric automobile, traditional lithium ion battery has been difficult to meet electric automobile high-energy close
The requirement of degree, the battery system in the urgent need to developing higher energy density.Lithium-air battery is because of the specific capacity and energy of its superelevation
Density obtains everybody extensive concern, and its theoretical energy density is up to 11430Wh/kg (not including oxygen), and it is one kind with gold
Category lithium is used as negative pole, battery of the oxygen in air as anode reactant.Because the active substance oxygen sources of positive pole are in sky
In gas, can from environment direct access and without being stored in inside battery, possess higher energy compared with lithium ion battery close
Degree, is just becoming in recent years the research and development focus in global range.
Lithium-air battery generally comprises negative pole, three parts of electrolyte and positive pole, mainly can be divided according to electrolyte difference
For water system and nonaqueous lithium air cell.The basic functional principle of water system lithium-air battery is that upon discharging generation oxygen reduction is anti-
Answer (ORR), now become lithium ion after the lithium metal release electronics of negative pole, lithium ion reaches positive pole through electrolyte, with oxygen,
The electronics that water and external circuit transmission come is combined and generates Lithium hydrate, and is dissolved in the electrolytic solution；When charging, by above-mentioned reaction
, there is oxygen reaction of formation (OER) in reversible carrying out.In water system lithium-air battery, due to the lithium metal and electrolyte of negative pole
In water violent reaction can occur, it is therefore desirable to lithium metal is protected, the reaction of lithium metal and water is prevented.At present, protect
The conventional method of shield lithium metal is to completely cut off metal lithium sheet and aqueous electrolyte using one layer of ceramic solid electrolyte LISICON,
Solid electrolyte LISICON can either conducting lithium ions, lithium metal can be prevented again to react with water.
At present, common problem is in this kind of solid electrolyte, and its conductivity at room temperature is than relatively low, and material is past
It is crisp toward comparing, it usually needs to reach certain thickness (more than 100 microns), just can guarantee that made potsherd has enough
Mechanical strength, does not rupture in use.And thickness increase means that the resistance of solid electrolyte membrane increases, under ion conductivity
Drop, and then greatly limit this electrolytelike application.Therefore, one kind is needed to be designed to deal with solid state electrolysis in association area
Contradiction between matter ion conductivity and mechanical strength.
The content of the invention
For the disadvantages described above or Improvement requirement of prior art, the invention provides a kind of solid electrolyte membrane, its preparation
Method and application, its object is to by the way that porous ceramic layer and solid-state electrolyte layer are combined, there is provided a kind of ionic conduction performance
The good and enough solid electrolyte membranes of mechanical strength, are applied to prepare lithium-air battery, thus solve existing solid electrolyte membrane
Contradiction between ionic conduction performance and mechanical strength, is applied to prepare that lithium-air battery internal resistance is high, the technology that performance is not good is asked
Topic.
For achieving the above object, according to one aspect of the present invention, there is provided a kind of solid electrolyte membrane, including solid-state electricity
Solution matter layer and porous ceramic layer, the solid-state electrolyte layer thickness between 0.5 micron to 10 microns, the porous ceramicss thickness
Between 100 microns to 300 microns, the solid-state electrolyte layer uniform fold is on porous ceramic layer for degree.
Preferably, the solid electrolyte membrane, the conductivity at room temperature of its solid-state electrolyte layer is 10-5To 10-6West gate
Son/centimetre.
Preferably, the solid electrolyte membrane, its material for stating solid-state electrolyte layer is NASICON type lithium ion conductors
Li1+xTi2-xMx(PO4)3、Li1+xGe2-xMx(PO4)3(0.1<x<0.7, M=Al, Ga, In, Sc), Ca-Ti ore type lithium ion conductor
Li3xLa(2/3)-xTiO3(0<x<0.16), LISICON types lithium ion conductor Li14ZnGe4O16Or carbuncle type lithium ion conductor
Li5La3M2O12(M=Ta, Nb).
Preferably, the solid electrolyte membrane, the flexural strength of its porous ceramic layer is in 80N/mm2To 170N/mm2It
Between.
Preferably, the solid electrolyte membrane, its porous ceramic layer be obtained using pore creating material porous oxidation zircon ceramic,
The ceramic super-filtering film of mesoporous silica gel, bilateral anodised aluminium or gradient pore-size distribution.
It is another aspect of this invention to provide that there is provided a kind of preparation method of described solid electrolyte membrane including following
Step：
(1) preparation of solid electrolyte presoma：According to the element ratio of target solid electrolyte by the original of respective element
Material is dispersed in organic solvent, and drying is obtained the mixed uniformly powder of the raw material, by the powder at 500 DEG C to 700
Sinter at DEG C and the solid electrolyte precursor powder is obtained；
(2) preparation of solid electrolyte target material：Obtained solid electrolyte precursor powder in step (1) is added into it
The binding agent of quality 1% to 10%, it is tabletted under 200MPa to 300MPa forcing presses, sinter at 900 DEG C to 1200 DEG C
Prepared solid electrolyte target material；
(3) porous ceramicss substrate plated film：With porous ceramicss as film forming substrate, with the solid electrolyte prepared in step (2)
Target material is target, using the method for magnetron sputtering, the thin film of uniform plating last layer solid electrolyte on porous ceramicss is made
Obtain the solid electrolyte membrane.
Preferably, the preparation method, the raw material described in its step (1) is oxide, the carbonate chemical combination of respective element
Thing and/or phosphate compoundss.
Preferably, the preparation method, the binding agent described in its step (2) is the polyvinyl alcohol of mass fraction 1% to 5%
Or the ethanol solution of polyvinyl butyral resin.
The solid electrolyte membrane that the present invention is provided, can be applicable to the preparation of lithium-air battery.
Using the lithium-air battery of the solid electrolyte membrane, including lithium anode, the solid electrolyte membrane, electrolysis
Liquid and porous anode；The porous ceramic layer of the solid electrolyte membrane, is full of electrolyte in its hole；The solid electrolyte membrane
It is arranged between lithium anode and porous anode, isolates the lithium anode and porous anode.
In general, by the contemplated above technical scheme of the present invention compared with prior art, can obtain down and show
Beneficial effect：The infiltration of oxygen and water is prevented while passing to lithium ion due to solid-state electrolyte layer, and porous ceramic layer has
Penetrating pore passage structure, electric conductivity is good in the case of having electrolyte therebetween, by the way that magnetron sputtering is by porous ceramic layer and consolidates
State dielectric substrate is combined together so that the solid electrolyte membrane that the present invention is provided, relative to the solid electrolyte of prior art
Film had both had enough mechanical strengths, and ionic conduction performance is greatly improved.The solid electrolyte membrane lithium ion that the present invention is provided
Conducting power is good, high mechanical strength, water proof oxygen barrier, preparation process is simple, low cost.Using the solid electrolyte that the present invention is provided
Film preparation lithium-air battery, internal resistance is significantly less than existing lithium-air battery, makes battery performance obtain larger raising.
Description of the drawings
Fig. 1 is the solid electrolyte membrane structural representation that the present invention is provided；
Fig. 2 is the lithium-air battery structural representation that the present invention is provided.
In all of the figs, identical reference be used for represent identical element or structure, wherein：
1 is solid-state electrolyte layer；2 is porous ceramic layer；3 is the penetrating pore passage structure of porous ceramic layer；4 is solid state electrolysis
Plasma membrane；5 is lithium anode；6 is porous anode；7 is electrolyte.
Specific embodiment
In order that the objects, technical solutions and advantages of the present invention become more apparent, it is right below in conjunction with drawings and Examples
The present invention is further elaborated.It should be appreciated that specific embodiment described herein is only to explain the present invention, and
It is not used in the restriction present invention.As long as additionally, technical characteristic involved in invention described below each embodiment
Not constituting conflict each other just can be mutually combined.
The solid electrolyte membrane that the present invention is provided, as shown in figure 1, including solid-state electrolyte layer and porous ceramic layer, it is described
Between 0.5 micron to 10 microns, the flexural strength of the porous ceramic layer is in 80N/mm for solid-state electrolyte layer thickness2Extremely
170N/mm2Between, it is preferable that its electrical conductivity is 10-5To 10-6Siemens/cm, the porous ceramic layer thickness is at 100 microns
To between 300 microns, the solid-state electrolyte layer uniform fold is on porous ceramic layer.
The material of the solid-state electrolyte layer, preferably NASICON types lithium ion conductor Li1+xTi2-xMx(PO4)3、Li1+ xGe2-xMx(PO4)3(0.1<x<0.7, M=Al, Ga, In, Sc), Ca-Ti ore type lithium ion conductor Li3xLa(2/3)-xTiO3(0<x<
0.16), LISICON types lithium ion conductor Li14ZnGe4O16, carbuncle type lithium ion conductor Li5La3M2O12(M=Ta, Nb).
The porous ceramic layer is porous oxidation zircon ceramic, mesoporous silica gel, the bilateral anodic oxidation obtained using pore creating material
The ceramic super-filtering film of aluminum or gradient pore-size distribution.The porous ceramic layer has penetrating pore passage structure.
The solid electrolyte membrane that the present invention is provided, its preparation method is comprised the following steps：
(1) preparation of solid electrolyte presoma：According to the element ratio of target solid electrolyte by the original of respective element
Material is dispersed in organic solvent, and drying is obtained the mixed uniformly powder of the raw material, by 500 DEG C to 700 DEG C of the powder
Sintering is obtained the solid electrolyte precursor powder；The raw material is the oxide of respective element, carbonate compound and/or
Phosphate compoundss；The preferred dehydrated alcohol of the organic solvent.
(2) preparation of solid electrolyte target material：Obtained solid electrolyte precursor powder in step (1) is added into it
The binding agent of quality 1% to 10%, binding agent is preferably the polyvinyl alcohol that mass fraction is 1% to 5% or polyvinyl alcohol contracting
The ethanol solution of butyraldehyde, it is tabletted under 200MPa to 300MPa forcing presses, sinter at 900 DEG C to 1200 DEG C and solid-state is obtained
Electrolyte target material material；
(3) porous ceramicss substrate plated film：With porous ceramicss as film forming substrate, with the solid electrolyte prepared in step (2)
Target material is target, using the method for magnetron sputtering, the thin film of uniform plating last layer solid electrolyte on porous ceramicss is made
Obtain the solid electrolyte membrane.
The solid electrolyte film thickness is generally less than 10 microns, so that porous ceramicss substrate side is completely covered as mark
Standard, film thickness is adjusted by controlling the magnetron sputtering time.The solid electrolyte membrane, under the conditions of ensureing uniformly, more
Thin its resistance is lower, and performance is better.
The distance between target and chip bench are preferably 10 to 15cm during sputter coating, and sputter coating is target and chip bench
Angle be 30 ° to 45 °, during sputter coating in vacuum chamber argon pressure be 0.5 to 2Pa, radio-frequency power supply work(during sputter coating
Rate is 50W to 200W.
The solid electrolyte membrane that the present invention is provided, can be applicable to the preparation of lithium-air battery.
A kind of lithium-air battery, as shown in Fig. 2 including lithium anode, solid electrolyte membrane, electrolyte and porous just
Pole；The porous ceramic layer of the solid electrolyte membrane, is full of electrolyte in its hole；The solid electrolyte membrane is arranged on lithium metal
Between negative pole and porous anode, isolate the lithium anode and porous anode.Preferably, the lithium anode is arranged on institute
The how empty ceramic layer side of solid electrolyte membrane is stated, the porous anode is arranged on the solid-state electrolyte layer side.
It is below embodiment：
Embodiment 1
A kind of solid electrolyte membrane, including solid-state electrolyte layer and porous ceramic layer, the solid-state electrolyte layer thickness exists
1.8 microns, the flexural strength of the porous ceramic layer is 100N/mm2, its lithium ion conductivity is 6.0 × 10-5Siemens/
Centimetre, the porous ceramic layer thickness is 170 microns, and the solid-state electrolyte layer uniform fold is on porous ceramic layer.
The material of the solid-state electrolyte layer is Ca-Ti ore type lithium ion conductor Li3xLa(2/3)-xTiO3(x=0.1, i.e.,
Li0.3La0.57TiO3, hereinafter referred to as LLTO).
The porous ceramic layer is bilateral anodised aluminium.
The solid electrolyte membrane, its preparation method is comprised the following steps：
(1) preparation of solid electrolyte presoma：By chemical formula Li3xLa(2/3)-xTiO3(x=0.1) (i.e.
Li0.3La0.57TiO3) in Li, La, Ti stoichiometric proportion 0.3:0.57:1, choose Li2CO3、La2O3、TiO2As raw material, its
Middle Li2CO3Excessive 5% (mass fraction), with 6 hour post-dryings of speed ball milling of 180r/min in anhydrous ethanol medium, system
The mixed uniformly powder of the raw material is obtained, the powder is calcined 10 hours in 600 DEG C of air, the solid electrolyte is obtained
Precursor powder.
(2) preparation of solid electrolyte target material：It will be added in obtained solid electrolyte precursor powder in step (1)
The binder solution of quality 1%, the binder solution for polyvinyl alcohol that mass fraction is 5% ethanol solution,
It is tabletted under 200MPa forcing presses, to calcine 5 hours at 1000 DEG C, heating rate is 3 DEG C/min, and solid electrolyte target is obtained
Material；
(3) porous ceramicss substrate plated film：With a diameter of 25mm, thickness is 170 μm, and pore size is 200nm's to 300nm
Bilateral anodised aluminium potsherd is film forming substrate, with the middle solid electrolyte target material for preparing of step (2) as target, using magnetic
The method of control sputtering, the thin film of uniform plating last layer solid electrolyte, that is, be obtained the solid state electrolysis on bilateral anodised aluminium
Plasma membrane.
The distance between target and chip bench are 10cm during sputter coating, and sputter coating is that target is with the angle of chip bench
35 °, argon pressure is 1Pa in vacuum chamber during sputter coating, and radio-frequency power supply power is 150W during sputter coating, and plated film time is
8 hours.
Described solid electrolyte membrane, can be applicable to the preparation of lithium-air battery.
A kind of lithium-air battery, including lithium anode, the solid electrolyte membrane, electrolyte and porous anode；Institute
The porous ceramic layer of solid electrolyte membrane is stated, electrolyte is full of in its hole；The solid electrolyte membrane is arranged on lithium anode
And porous anode between, isolate the lithium anode and porous anode.The lithium anode is arranged on the solid state electrolysis
The how empty ceramic layer side of plasma membrane, the porous anode is arranged on the solid-state electrolyte layer side.It is prepared as follows：
In the glove box of argon gas atmosphere, the lithium piece that thickness is 0.5mm is encapsulated with the solid electrolyte membrane and Copper Foil
Firmly, lithium piece is contacted with the solid electrolyte membrane porous ceramic layer, and is infiltrated in 1mol/L lithium hexafluoro phosphate (LiPF6)-carbonic acid
In propylene (PC) electrolyte, meanwhile, ensure contact of the lithium piece with Copper Foil, the purple corroded with electrolyte resistance with one little nickel foam
Outer light-cured resin edge sealing, it is ensured that negative pole is sealed.After the completion of negative pole sealing, glove box is removed, it is solid in the solid electrolyte membrane
State dielectric substrate side, places the graphene sponge of porous, and with the phosphoric acid (H of 0.1mol/L3PO4) -1M lithium dihydrogen phosphates
(LiH2PO4) solution immersion graphene sponge, with a small pieces nickel foam as plus plate current-collecting body, constitute one and mix
Electrolyte lithium air cell is closed, (-) Li can be represented simply as | LiPF6-PC|LLTO@AAO|H3PO4-LiH2PO4| Graphene (+),
Discharged after standing 1 hour in atmosphere, electric current density is 0.2mA/cm2When, cell voltage is 3.62V, total cell weight
(weigh before electric discharge) for 0.38g, discharge capacity of the cell is 46mAh.
Embodiment 2
A kind of solid electrolyte membrane, including solid-state electrolyte layer and porous ceramic layer, the solid-state electrolyte layer thickness is 1
Micron, the flexural strength of the porous ceramic layer is in 100N/mm2, its lithium ion conductivity is 1.2 × 10-6Siemens/li
Rice, the porous ceramic layer thickness is 170 microns, and the solid-state electrolyte layer uniform fold is on porous ceramic layer.
The material of the solid-state electrolyte layer is, NASICON type lithium ion conductor Li1+yGe2-x-yTixAly(PO4)3(wherein
X=0.3, y=0.21, i.e. Li1.21Ge1.49Al0.21Ti0.3(PO4)3, hereinafter referred to as LGATP).
The porous ceramic layer is bilateral anodised aluminium.
The solid electrolyte membrane, its preparation method is comprised the following steps：
(1) preparation of solid electrolyte presoma：By chemical formula Li1.21Ge1.49Al0.21Ti0.3(PO4)3Middle Li, Ge, Al,
Ti、PO4Stoichiometric proportion 1.21:1.49:0.21:0.3:3, choose Li2CO3、GeO2、Al2O3、TiO2And NH4H2PO4As
Raw material, wherein Li2CO3Excessive 5% (mass fraction), in anhydrous ethanol medium with 6 hours of speed ball milling of 180r/min after
Drying, is obtained the mixed uniformly powder of the raw material, will calcine 10 hours at 500 DEG C of the powder, and the solid state electrolysis is obtained
Matter precursor powder.
(2) preparation of solid electrolyte target material：To add in obtained solid electrolyte precursor powder in step (1)
The binder solution of its quality 10%, the binder solution is the ethanol solution of the polyvinyl butyral resin of mass fraction 1%,
It is tabletted under 200MPa forcing presses, to calcine 5 hours at 900 DEG C, heating rate is 3 DEG C/min, and solid electrolyte is obtained
Target material；
(3) porous ceramicss substrate plated film：With a diameter of 25mm, thickness is 170 μm, and pore size is the double of 200-300nm
The pole alumina ceramic plate that activates yang is film forming substrate, with the middle solid electrolyte target material for preparing of step (2) as target, using magnetic control
The method of sputtering, the thin film of uniform plating last layer solid electrolyte, that is, be obtained the solid electrolyte on bilateral anodised aluminium
Film.
The distance between target and chip bench are 10cm during sputter coating, and sputter coating is that target is with the angle of chip bench
35 °, argon pressure is 2Pa in vacuum chamber during sputter coating, and radio-frequency power supply power is 100W during sputter coating, and plated film time is
10 hours.
The solid electrolyte membrane that the present invention is provided, can be applicable to the preparation of lithium-air battery.
A kind of lithium-air battery, including lithium anode, the solid electrolyte membrane, electrolyte and porous anode；Institute
The porous ceramic layer of solid electrolyte membrane is stated, electrolyte is full of in its hole；The solid electrolyte membrane is arranged on lithium anode
And porous anode between, isolate the lithium anode and porous anode.The lithium anode is arranged on the solid state electrolysis
The how empty ceramic layer side of plasma membrane, the porous anode is arranged on the solid-state electrolyte layer side.It is prepared as follows：
In the glove box of argon gas atmosphere, the lithium piece that thickness is 0.5mm is encapsulated with the solid electrolyte membrane and Copper Foil
Firmly, lithium piece is contacted with the solid electrolyte membrane porous ceramic layer, and is infiltrated in 1mol/L lithium hexafluoro phosphate (LiPF6)-carbonic acid
In propylene (PC) electrolyte, meanwhile, ensure contact of the lithium piece with Copper Foil, the purple corroded with electrolyte resistance with one little nickel foam
Outer light-cured resin edge sealing, it is ensured that negative pole is sealed.After the completion of negative pole sealing, glove box is removed, it is solid in the solid electrolyte membrane
State dielectric substrate side, places the graphene sponge of porous, and extra large with 1mol/L lithium chlorides (LiCl) solution immersion Graphene
Silk floss, with a small pieces nickel foam as plus plate current-collecting body, constitutes a mixed electrolyte lithium-air battery, can simple table
It is shown as (-) Li | LiPF6- PC | LGATP AAO | LiCl | Graphenes (+), discharged after standing 1 hour in atmosphere, electric current
When density is 0.05mA/cm2, cell voltage is 3.64V, and total cell weight (is weighed) for 0.45g before electric discharge, discharge capacity of the cell
For 39mAh.
Embodiment 3
A kind of solid electrolyte membrane, including solid-state electrolyte layer and porous ceramic layer, the solid-state electrolyte layer thickness exists
10 microns, the flexural strength of the porous ceramic layer is in 170N/mm2, its lithium ion conductivity is 5.2 × 10-5Siemens/li
Rice, the porous ceramic layer thickness is 300 microns, and the solid-state electrolyte layer uniform fold is on porous ceramic layer.
The material of the solid-state electrolyte layer is LISICON type lithium ion conductor Li14ZnGe4O16(hereinafter referred to as LZGO).
The porous ceramic layer is the porous oxidation zircon ceramic obtained using pore creating material.
The solid electrolyte membrane, its preparation method is comprised the following steps：
(1) preparation of solid electrolyte presoma：By chemical formula Li14ZnGe4O16The stoichiometric proportion 14 of middle Li, Zn, Ge:
1:4, choose Li2CO3、ZnO、GeO2As raw material, wherein Li2CO3Excessive 5% (mass fraction), in anhydrous ethanol medium with
6 hour post-dryings of speed ball milling of 180r/min, are obtained the mixed uniformly powder of the raw material, by the powder at 650 DEG C
Calcine 10 hours in air, the solid electrolyte precursor powder is obtained.
(2) preparation of solid electrolyte target material：To add in obtained solid electrolyte precursor powder in step (1)
The binder solution of its quality 4%, the binder solution is the ethanol solution of the polyvinyl butyral resin of mass fraction 3%,
It is tabletted under 300MPa forcing presses, to calcine 5 hours at 1100 DEG C, heating rate is 3 DEG C/min, and solid electrolyte is obtained
Target material；
(3) porous ceramicss substrate plated film：With a diameter of 25mm, thickness is 300 microns, and pore size is 1.5 microns many
Hole zirconia ceramicss are film forming substrate, with the middle solid electrolyte target material for preparing of step (2) as target, using magnetron sputtering
Method, the thin film of uniform plating last layer solid electrolyte, that is, be obtained the solid electrolyte membrane on bilateral anodised aluminium.
The distance between target and chip bench are 10cm during sputter coating, and sputter coating is that target is with the angle of chip bench
35 °, argon pressure is 1Pa in vacuum chamber during sputter coating, and radio-frequency power supply power is 200W during sputter coating, and plated film time is
20 hours.
The solid electrolyte membrane that the present invention is provided, can be applicable to the preparation of lithium-air battery.
A kind of lithium-air battery, including lithium anode, the solid electrolyte membrane, electrolyte and porous anode；Institute
The porous ceramic layer of solid electrolyte membrane is stated, electrolyte is full of in its hole；The solid electrolyte membrane is arranged on lithium anode
And porous anode between, isolate the lithium anode and porous anode.The lithium anode is arranged on the solid state electrolysis
The how empty ceramic layer side of plasma membrane, the porous anode is arranged on the solid-state electrolyte layer side.It is prepared as follows：
In the glove box of argon gas atmosphere, the lithium piece that thickness is 0.5mm is encapsulated with the solid electrolyte membrane and Copper Foil
Firmly, lithium piece is contacted with the solid electrolyte membrane porous ceramic layer, and is infiltrated in 1mol/L lithium hexafluoro phosphate (LiPF6)-carbonic acid
In propylene (PC) electrolyte, meanwhile, ensure contact of the lithium piece with Copper Foil, the purple corroded with electrolyte resistance with one little nickel foam
Outer light-cured resin edge sealing, it is ensured that negative pole is sealed.After the completion of negative pole sealing, glove box is removed, it is solid in the solid electrolyte membrane
State dielectric substrate side, places the graphene sponge of porous, and with the phosphoric acid (H of 0.1mol/L3PO4) -1M lithium dihydrogen phosphates
(LiH2PO4) solution immersion graphene sponge, with a small pieces nickel foam as plus plate current-collecting body, constitute one and mix
Electrolyte lithium air cell is closed, (-) Li can be represented simply as | LiPF6-PC|LZGO@ZrO2|H3PO4-LiH2PO4| Graphene
(+), is discharged after standing 1 hour in atmosphere, and electric current density is 0.05mA/cm2When, cell voltage is 3.45V, and battery is total
Weight is 0.45g (weighing before electric discharge), and discharge capacity of the cell is 15mAh.
Embodiment 4
A kind of solid electrolyte membrane, including solid-state electrolyte layer and porous ceramic layer, the solid-state electrolyte layer thickness exists
0.5 micron, the flexural strength of the porous ceramic layer is in 80N/mm2, its lithium ion conductivity is 2.6 × 10-5Siemens/li
Rice, the porous ceramic layer thickness is 100 microns, and the solid-state electrolyte layer uniform fold is on porous ceramic layer.
The material of the solid-state electrolyte layer is carbuncle type lithium ion conductor Li5La3Ta2O12(hereinafter referred to as LLTAO).
The porous ceramic layer is the ceramic super-filtering film of gradient pore-size distribution.
The solid electrolyte membrane, its preparation method is comprised the following steps：
(1) preparation of solid electrolyte presoma：By chemical formula Li5La3Ta2O12The stoichiometric proportion 5 of middle Li, La, Ta:
3:2, choose Li2CO3、La2O3、Ta2O5As raw material, wherein Li2CO3Excessive 5% (mass fraction), in anhydrous ethanol medium
With 6 hour post-dryings of speed ball milling of 180r/min, the mixed uniformly powder of the raw material is obtained, by the powder 700
Calcine 10 hours in DEG C air, the solid electrolyte precursor powder is obtained.
(2) preparation of solid electrolyte target material：To add in obtained solid electrolyte precursor powder in step (1)
The binder solution of its quality 4%, the binder solution is the ethanol solution of the polyvinyl butyral resin of mass fraction 3%,
It is tabletted under 250MPa forcing presses, to calcine 5 hours at 1200 DEG C, heating rate is 3 DEG C/min, and solid electrolyte is obtained
Target material；
(3) porous ceramicss substrate plated film：With a diameter of 25mm, thickness is 150 μm, and pore-size distribution surpasses for the ceramics of 2-50nm
Filter membrane is film forming substrate, and in the little side plated film in aperture, the solid electrolyte target material prepared with step (2) is adopted as target
With the method for magnetron sputtering, the thin film of uniform plating last layer solid electrolyte, that is, be obtained the solid-state on bilateral anodised aluminium
Dielectric film.
The distance between target and chip bench are 10cm during sputter coating, and sputter coating is that target is with the angle of chip bench
35 °, argon pressure is 1Pa in vacuum chamber during sputter coating, and radio-frequency power supply power is 60W during sputter coating, and plated film time is 2
Hour.
The solid electrolyte membrane that the present invention is provided, can be applicable to the preparation of lithium-air battery.
A kind of lithium-air battery, including lithium anode, the solid electrolyte membrane, electrolyte and porous anode；Institute
The porous ceramic layer of solid electrolyte membrane is stated, electrolyte is full of in its hole；The solid electrolyte membrane is arranged on lithium anode
And porous anode between, isolate the lithium anode and porous anode.The lithium anode is arranged on the solid state electrolysis
The how empty ceramic layer side of plasma membrane, the porous anode is arranged on the solid-state electrolyte layer side.It is prepared as follows：
In the glove box of argon gas atmosphere, the lithium piece that thickness is 0.5mm is encapsulated with the solid electrolyte membrane and Copper Foil
Firmly, lithium piece is contacted with the solid electrolyte membrane porous ceramic layer, and is infiltrated in 1mol/L lithium hexafluoro phosphate (LiPF6)-carbonic acid
In propylene (PC) electrolyte, meanwhile, ensure contact of the lithium piece with Copper Foil, the purple corroded with electrolyte resistance with one little nickel foam
Outer light-cured resin edge sealing, it is ensured that negative pole is sealed.After the completion of negative pole sealing, glove box is removed, it is solid in the solid electrolyte membrane
State dielectric substrate side, places the graphene sponge of porous, and with lithium chloride (LiCl) the solution immersion Graphene of 1mol/L
Sponge, with a small pieces nickel foam as plus plate current-collecting body, constitutes a mixed electrolyte lithium-air battery, can be simple
It is expressed as (-) Li | LiPF6- PC | LLTAO ultrafilter membranes | LiCl | Graphenes (+), discharged after standing 1 hour in atmosphere,
Electric current density is 0.02mA/cm2When, cell voltage is 3.54V, and total cell weight (is weighed) for 0.45g before electric discharge, battery discharge
Capacity is 9mAh.
Embodiment 5
A kind of solid electrolyte membrane, including solid-state electrolyte layer and porous ceramic layer, the solid-state electrolyte layer thickness exists
0.5 micron, the flexural strength of the porous ceramic layer is in 110N/mm2, its lithium ion conductivity is 5.8 × 10-5Siemens/
Centimetre, the porous ceramic layer thickness is 260 microns, and the solid-state electrolyte layer uniform fold is on porous ceramic layer.
The material of the solid-state electrolyte layer is Ca-Ti ore type lithium ion conductor Li3xLa(2/3)-xTiO3(x=0.1, i.e.,
Li0.3La0.57TiO3, hereinafter referred to as LLTO).
The potsherd that the porous ceramic layer is pressed into for mesoporous silica gel.
The solid electrolyte membrane, its preparation method is comprised the following steps：
(1) preparation of solid electrolyte presoma：By chemical formula Li3xLa(2/3)-xTiO3(x=0.1) (i.e.
Li0.3La0.57TiO3) in Li, La, Ti stoichiometric proportion 0.3:0.57:1, choose Li2CO3、La2O3、TiO2As raw material, its
Middle Li2CO3Excessive 5% (mass fraction), with 6 hour post-dryings of speed ball milling of 180r/min in anhydrous ethanol medium, system
The mixed uniformly powder of the raw material is obtained, the powder is calcined 10 hours in 600 DEG C of air, the solid electrolyte is obtained
Precursor powder.
(2) preparation of solid electrolyte target material：It will be added in obtained solid electrolyte precursor powder in step (1)
The binder solution of quality 1%, the binder solution for polyvinyl alcohol that mass fraction is 5% ethanol solution,
It is tabletted under 200MPa forcing presses, to calcine 5 hours at 1000 DEG C, heating rate is 3 DEG C/min, and solid electrolyte target is obtained
Material；
(3) porous ceramicss substrate plated film：With a diameter of 20mm, thickness is 260 μm, and pore size is the mesoporous of 25nm or so
Silica gel potsherd is film forming substrate, with the middle solid electrolyte target material for preparing of step (2) as target, using the side of magnetron sputtering
Method, the thin film of uniform plating last layer solid electrolyte, that is, be obtained the solid electrolyte membrane on bilateral anodised aluminium.
The distance between target and chip bench are 10cm during sputter coating, and sputter coating is that target is with the angle of chip bench
35 °, argon pressure is 1Pa in vacuum chamber during sputter coating, and radio-frequency power supply power is 80W during sputter coating, and plated film time is 5
Hour.
The solid electrolyte membrane that the present invention is provided, can be applicable to the preparation of lithium-air battery.
A kind of lithium-air battery, including lithium anode, the solid electrolyte membrane, electrolyte and porous anode；Institute
The porous ceramic layer of solid electrolyte membrane is stated, electrolyte is full of in its hole；The solid electrolyte membrane is arranged on lithium anode
And porous anode between, isolate the lithium anode and porous anode.The lithium anode is arranged on the solid state electrolysis
The how empty ceramic layer side of plasma membrane, the porous anode is arranged on the solid-state electrolyte layer side.It is prepared as follows：
In the glove box of argon gas atmosphere, the lithium piece that thickness is 0.5mm is encapsulated with the solid electrolyte membrane and Copper Foil
Firmly, lithium piece is contacted with the solid electrolyte membrane porous ceramic layer, and is infiltrated in 1mol/L lithium hexafluoro phosphate (LiPF6)-carbonic acid
In propylene (PC) electrolyte, meanwhile, ensure contact of the lithium piece with Copper Foil, the purple corroded with electrolyte resistance with one little nickel foam
Outer light-cured resin edge sealing, it is ensured that negative pole is sealed.After the completion of negative pole sealing, glove box is removed, it is solid in the solid electrolyte membrane
State dielectric substrate side, places the graphene sponge of porous, and with lithium chloride (LiCl) the solution immersion Graphene of 1mol/L
Sponge, with a small pieces nickel foam as plus plate current-collecting body, constitutes a mixed electrolyte lithium-air battery, can be simple
It is expressed as (-) Li | LiPF6- PC | LLTO mesoporous silica gels | LiCl | Graphenes (+), put after standing 1 hour in atmosphere
Electricity, electric current density is 0.02mA/cm2When, cell voltage is 3.49V, and total cell weight (is weighed) for 0.45g before electric discharge, battery
Discharge capacity is 11mAh.
As it will be easily appreciated by one skilled in the art that the foregoing is only presently preferred embodiments of the present invention, not to
The present invention, all any modification, equivalent and improvement made within the spirit and principles in the present invention etc. are limited, all should be included
Within protection scope of the present invention.
Claims (10)
1. a kind of solid electrolyte membrane, it is characterised in that including solid-state electrolyte layer and porous ceramic layer, the solid electrolyte
Thickness degree between 0.5 micron to 10 microns, the porous ceramic layer thickness between 100 microns to 300 microns, the solid-state
On porous ceramic layer, the preparation method of the solid electrolyte membrane is comprised the following steps dielectric substrate uniform fold：
(1) preparation of solid-state electrolyte layer presoma：According to the element ratio of target solid-state electrolyte layer by the original of respective element
Material is dispersed in organic solvent, and drying is obtained the mixed uniformly powder of the raw material, by the powder at 500 DEG C to 700
Sinter at DEG C and the solid-state electrolyte layer precursor powder is obtained；
(2) preparation of solid-state electrolyte layer target material：Obtained solid-state electrolyte layer precursor powder in step (1) is added into it
The binding agent of quality 1% to 10%, it is tabletted under 200MPa to 300MPa forcing presses, sinter at 900 DEG C to 1200 DEG C
Prepared solid-state electrolyte layer target material；
(3) porous ceramicss substrate plated film：With porous ceramicss as film forming substrate, with the solid-state electrolyte layer target prepared in step (2)
Material is target, using the method for magnetron sputtering, the thin film of uniform plating last layer solid electrolyte on porous ceramicss is obtained
The solid electrolyte membrane.
2. solid electrolyte membrane as claimed in claim 1, it is characterised in that the room-temperature ion conductance of the solid-state electrolyte layer
Rate is 10-5To 10-6Siemens/cm.
3. solid electrolyte membrane as claimed in claim 2, it is characterised in that the material of the solid-state electrolyte layer is
NASICON type lithium ion conductor Li1+xTi2-xMx(PO4)3、Li1+xGe2-xMx(PO4)3, Ca-Ti ore type lithium ion conductor
Li3yLa(2/3)-yTiO3, LISICON type lithium ion conductor Li14ZnGe4O16Or carbuncle type lithium ion conductor Li5La3N2O12, its
In 0.1<x<0.7 and M=Al, Ga, In or Sc, 0<y<0.16, N=Ta or Nb.
4. solid electrolyte membrane as claimed in claim 1, it is characterised in that the flexural strength of the porous ceramic layer exists
80N/mm2To 170N/mm2Between.
5. solid electrolyte membrane as claimed in claim 4, it is characterised in that the porous ceramic layer is to be obtained using pore creating material
Porous oxidation zircon ceramic, mesoporous silica gel, the ceramic super-filtering film of bilateral anodised aluminium or gradient pore-size distribution.
6. the preparation method of the solid electrolyte membrane as described in claim 1 to 5 any one, it is characterised in that including following
Step：
(1) preparation of solid-state electrolyte layer presoma：According to the element ratio of target solid-state electrolyte layer by the original of respective element
Material is dispersed in organic solvent, and drying is obtained the mixed uniformly powder of the raw material, by the powder at 500 DEG C to 700
Sinter at DEG C and the solid-state electrolyte layer precursor powder is obtained；
(2) preparation of solid-state electrolyte layer target material：Obtained solid-state electrolyte layer precursor powder in step (1) is added into it
The binding agent of quality 1% to 10%, it is tabletted under 200MPa to 300MPa forcing presses, sinter at 900 DEG C to 1200 DEG C
Prepared solid-state electrolyte layer target material；
(3) porous ceramicss substrate plated film：With porous ceramicss as film forming substrate, with the solid-state electrolyte layer target prepared in step (2)
Material is target, using the method for magnetron sputtering, the thin film of uniform plating last layer solid electrolyte on porous ceramicss is obtained
The solid electrolyte membrane.
7. preparation method as claimed in claim 6, it is characterised in that the raw material described in step (1) for respective element oxidation
Thing, carbonate compound and/or phosphate compoundss.
8. preparation method as claimed in claim 6, it is characterised in that the binding agent described in step (2) is mass fraction 1%
Polyvinyl alcohol or the ethanol solution of polyvinyl butyral resin to 5%.
9. application of the solid electrolyte membrane as described in claim 1 to 5 any one in the preparation of lithium-air battery.
10. it is a kind of application as described in claim 1 to 5 any one solid electrolyte membrane lithium-air battery, it is characterised in that
Including lithium anode, the solid electrolyte membrane as described in claim 1 to 5, electrolyte and porous anode；The solid-state electricity
The porous ceramic layer of solution plasma membrane, is full of electrolyte in its hole；The solid electrolyte membrane is being arranged on lithium anode and porous just
Between pole, isolate the lithium anode and porous anode.
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| JP2016091995A (en) * | 2014-10-30 | 2016-05-23 | 株式会社デンソー | Lithium air battery and lithium air battery device |
| CN105742761B (en) * | 2016-02-29 | 2018-03-23 | 苏州大学 | A kind of full-solid lithium air battery and preparation method and application |
| CN106299467A (en) * | 2016-09-13 | 2017-01-04 | 清华大学 | Composite solid electrolyte and flexible all-solid-state battery and preparation method, wearable electronic |
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| CN108666613B (en) * | 2017-03-27 | 2020-09-08 | 华为技术有限公司 | Solid electrolyte structure, secondary battery and preparation method |
| CN107369848A (en) * | 2017-07-14 | 2017-11-21 | 北京化工大学 | A kind of composite electrolyte of sandwich structure and preparation method thereof |
| CN110635113B (en) * | 2019-08-16 | 2021-09-03 | 南方科技大学 | Lithium cathode or sodium cathode, and preparation method and application of lithium cathode or sodium cathode |
| CN111020504A (en) * | 2019-12-12 | 2020-04-17 | 河北大学 | Li1+xAlxGe2-x(PO4)3Preparation method and application of solid electrolyte film |
| CN111028977B (en) * | 2019-12-24 | 2021-04-20 | 东北大学 | Double-layer composite proton conductor material and preparation method thereof |
| JP7035281B2 (en) * | 2019-12-27 | 2022-03-14 | 昭和電工株式会社 | Lithium Ion Conductive Oxides and Their Applications |
| KR20210102738A (en) * | 2020-02-12 | 2021-08-20 | 삼성전자주식회사 | Composite solid electrolyte, preparaing method thereof, and electrochemical battery including the composite solid electrolyte |
| CN111430806B (en) * | 2020-03-03 | 2021-09-24 | 桂林电子科技大学 | Fluorophosphate film solid electrolyte and preparation method and application thereof |
| CN111430787B (en) * | 2020-03-03 | 2022-03-15 | 桂林电子科技大学 | Composite film solid electrolyte and preparation method and application thereof |
| US20220069270A1 (en) * | 2020-09-03 | 2022-03-03 | GM Global Technology Operations LLC | Battery, methods of manufacture thereof and articles comprising the same |
| CN112490411B (en) * | 2020-11-25 | 2022-04-12 | 哈尔滨工业大学 | Method for protecting lithium metal negative electrode through in-situ film forming |
| CN114950589B (en) * | 2022-05-27 | 2024-02-09 | 复旦大学 | Application of MCT/AAO heterogeneous ultrathin film in light-operated bidirectional adjustable ion transmission |
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| JP5153065B2 (en) * | 2005-08-31 | 2013-02-27 | 株式会社オハラ | Lithium ion secondary battery and solid electrolyte |
| CN100500615C (en) * | 2006-06-27 | 2009-06-17 | 哈尔滨工业大学 | Improved coating method for preparing membrane of oxide ceramics |
| DE102010030197A1 (en) * | 2010-06-17 | 2011-12-22 | Sb Limotive Company Ltd. | Lithium-ion cell |
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| KR101422908B1 (en) * | 2012-04-02 | 2014-07-23 | 삼성정밀화학 주식회사 | Electrolyte for Lithium Ion Secondary Battery and Lithium Ion Secondary Battery Comprising The Same |
| KR101484503B1 (en) * | 2012-10-29 | 2015-01-30 | 한국에너지기술연구원 | Cathode Catalyst for Lithium-Air Battery, Method of Manufacturing the Same, and Lithium-Air Battery Comprising the Same |
| US9876247B2 (en) * | 2012-11-15 | 2018-01-23 | Corning Incorporated | Solid ceramic electrolytes |
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