CN104103873A - 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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- CN104103873A CN104103873A CN201410290828.5A CN201410290828A CN104103873A CN 104103873 A CN104103873 A CN 104103873A CN 201410290828 A CN201410290828 A CN 201410290828A CN 104103873 A CN104103873 A CN 104103873A
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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
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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 specifically, relate to a kind of solid electrolyte membrane and application thereof.
Background technology
Be accompanied by the fast development of electric automobile, traditional lithium ion battery has been difficult to meet the requirement of electric automobile high-energy-density, in the urgent need to developing the more battery system of high-energy-density.The extensive concern that lithium-air battery obtains everybody because of specific capacity and the energy density of its superelevation, its theoretical energy density is up to 11430Wh/kg (not comprising oxygen), it is a kind ofly to using lithium metal as negative pole, and airborne oxygen is as the battery of anode reactant.Because anodal active material oxygen derives from air, can from environment, directly obtain and need not be stored in inside battery, compare with lithium ion battery and possess higher energy density, just becoming in recent years the research and development focus in global range.
Lithium-air battery generally comprises negative pole, electrolyte and anodal three parts, according to electrolyte difference, mainly can be divided into water system and nonaqueous lithium air cell.The basic functional principle of water system lithium-air battery is that oxygen reduction reaction (ORR) occurs when electric discharge, now the lithium metal of negative pole becomes lithium ion after discharging electronics, lithium ion arrives anodal through electrolyte, the electronics coming with oxygen, water and external circuit transmission is combined and is generated lithium hydroxide, and is dissolved in electrolyte; When charging, by reversible the carrying out of above-mentioned reaction, there is oxygen reaction of formation (OER).In water system lithium-air battery, because the lithium metal of negative pole, with the water in electrolyte, violent reacting can occur, therefore need to protect lithium metal, prevention lithium metal reacts with water.At present, protection lithium metal conventional method is to completely cut off metal lithium sheet and aqueous electrolyte with the ceramic solid electrolyte LISICON of one deck, and solid electrolyte LISICON can either conductive lithium ion, can stop again lithium metal and water to react.
At present, in this class solid electrolyte, ubiquitous problem is, its conductivity at room temperature is lower, and material is often more crisp, conventionally need to reach certain thickness (being greater than 100 microns), the made potsherd of guarantee has enough mechanical strengths, does not in use break.And thickness increase means that the resistance of solid electrolyte membrane increases, ionic conduction ability declines, and then has limited greatly this electrolytelike application.Therefore, in association area, need a kind of design to solve the contradiction between solid electrolyte ionic conduction ability and mechanical strength.
Summary of the invention
Above defect or Improvement requirement for prior art, the invention provides a kind of solid electrolyte membrane, its preparation method and application, its object is by porous ceramic layer and solid-state electrolyte layer is compound, the solid electrolyte membrane that a kind of ionic conduction performance is good and mechanical strength is enough is provided, be applied to prepare lithium-air battery, solve thus the contradiction between existing solid electrolyte membrane ionic conduction performance and mechanical strength, be applied to prepare the technical problem that lithium-air battery internal resistance is high, performance is not good.
For achieving the above object, according to one aspect of the present invention, a kind of solid electrolyte membrane is provided, comprise solid-state electrolyte layer and porous ceramic layer, described solid electrolyte layer thickness is between 0.5 micron to 10 microns, described porous ceramic layer thickness is between 100 microns to 300 microns, and described solid-state electrolyte layer uniform fold is on porous ceramic layer.
Preferably, described solid electrolyte membrane, the conductivity at room temperature of its solid-state electrolyte layer is 10
-5to 10
-6siemens/cm.
Preferably, described solid electrolyte membrane, its material of stating solid-state electrolyte layer is NASICON type lithium ion conductor Li
1+xti
2-xm
x(PO
4)
3, Li
1+xge
2-xm
x(PO
4)
3(0.1<x<0.7, M=Al, Ga, In, Sc), Ca-Ti ore type lithium ion conductor Li
3xla
(2/3)-xtiO
3(0<x<0.16), LISICON type lithium ion conductor Li
14znGe
4o
16or carbuncle type lithium ion conductor Li
5la
3m
2o
12(M=Ta, Nb).
Preferably, described solid electrolyte membrane, the flexural strength of its porous ceramic layer is at 80N/mm
2to 170N/mm
2between.
Preferably, described solid electrolyte membrane, its porous ceramic layer is the ceramic super-filtering film of the porous oxidation zircon ceramic, mesoporous silica gel, bilateral anodised aluminium or the gradient pore-size distribution that utilize pore creating material to obtain.
According to another aspect of the present invention, a kind of preparation method of described solid electrolyte membrane is provided, comprise the following steps:
(1) preparation of solid electrolyte presoma: the raw material of respective element is dispersed in organic solvent according to the element ratio of target solid electrolyte, oven dry makes the mixed uniformly powder of described raw material, and described powder sintering at 500 ℃ to 700 ℃ is made to described solid electrolyte precursor powder;
(2) preparation of solid electrolyte target material: the binding agent that the solid electrolyte precursor powder making in step (1) is added to its quality 1% to 10%, under 200MPa to 300MPa forcing press, be pressed into sheet, at 900 ℃ to 1200 ℃, sintering makes solid electrolyte target material;
(3) porous ceramic substrate plated film: take porous ceramic as film forming substrate, the middle solid electrolyte target material of preparing of the step (2) of take is target, the method that adopts magnetron sputtering, by evenly plating the film of one deck solid electrolyte on porous ceramic, makes described solid electrolyte membrane.
Preferably, described preparation method, oxide, carbonate compound and/or phosphate compounds that the described raw material of its step (1) is respective element.
Preferably, described preparation method, the described binding agent of its step (2) is the polyvinyl alcohol of mass fraction 1% to 5% or the ethanolic solution of polyvinyl butyral resin.
Solid electrolyte membrane provided by the invention, can be applicable to the preparation of lithium-air battery.
Apply the lithium-air battery of described solid electrolyte membrane, comprise lithium anode, described solid electrolyte membrane, electrolyte and porous anode; The porous ceramic layer of described solid electrolyte membrane, is full of electrolyte in its hole; Described solid electrolyte membrane is arranged between lithium anode and porous anode, isolates described lithium anode and porous anode.
In general, the above technical scheme of conceiving by the present invention compared with prior art, , can obtain following beneficial effect: when lithium ion can be passed to due to solid-state electrolyte layer, stop the infiltration of oxygen G&W, and porous ceramic layer has penetrating pore passage structure, there is in the situation of electrolyte electric conductivity good therebetween, by magnetron sputtering, porous ceramic layer and solid-state electrolyte layer are combined, make solid electrolyte membrane provided by the invention, solid electrolyte membrane with respect to prior art had both had enough mechanical strengths, ionic conduction performance has raising greatly.Solid electrolyte membrane lithium ion conduction ability provided by the invention is good, mechanical strength is high, water proof oxygen barrier, preparation technology is simple, cost is low.Apply solid electrolyte film preparation lithium-air battery provided by the invention, internal resistance is significantly less than existing lithium-air battery, makes battery performance obtain larger raising.
Accompanying drawing explanation
Fig. 1 is solid electrolyte membrane structural representation provided by the invention;
Fig. 2 is lithium-air battery structural representation provided by the invention.
In institute's drawings attached, identical Reference numeral is used for representing 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 electrolyte membrane; 5 is lithium anode; 6 is porous anode; 7 is electrolyte.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.In addition,, in each execution mode of described the present invention, involved technical characterictic just can not combine mutually as long as do not form each other conflict.
Solid electrolyte membrane provided by the invention, as shown in Figure 1, comprises solid-state electrolyte layer and porous ceramic layer, and described solid electrolyte layer thickness is between 0.5 micron to 10 microns, and the flexural strength of described porous ceramic layer is at 80N/mm
2to 170N/mm
2between, preferably, its conductivity is 10
-5to 10
-6siemens/cm, described porous ceramic layer thickness is between 100 microns to 300 microns, and described solid-state electrolyte layer uniform fold is on porous ceramic layer.
The material of described solid-state electrolyte layer, is preferably NASICON type lithium ion conductor Li
1+xti
2-xm
x(PO
4)
3, Li
1+xge
2-xm
x(PO
4)
3(0.1<x<0.7, M=Al, Ga, In, Sc), Ca-Ti ore type lithium ion conductor Li
3xla
(2/3)-xtiO
3(0<x<0.16), LISICON type lithium ion conductor Li
14znGe
4o
16, carbuncle type lithium ion conductor Li
5la
3m
2o
12(M=Ta, Nb).
Described porous ceramic layer is the ceramic super-filtering film of the porous oxidation zircon ceramic, mesoporous silica gel, bilateral anodised aluminium or the gradient pore-size distribution that utilize pore creating material to obtain.Described porous ceramic layer has penetrating pore passage structure.
Solid electrolyte membrane provided by the invention, its preparation method, comprises the following steps:
(1) preparation of solid electrolyte presoma: the raw material of respective element is dispersed in organic solvent according to the element ratio of target solid electrolyte, oven dry makes the mixed uniformly powder of described raw material, and 500 ℃ to 700 ℃ sintering of described powder are made to described solid electrolyte precursor powder; Described raw material is oxide, carbonate compound and/or the phosphate compounds of respective element; The preferred absolute ethyl alcohol of described organic solvent.
(2) preparation of solid electrolyte target material: the binding agent that the solid electrolyte precursor powder making in step (1) is added to its quality 1% to 10%, it is 1% to 5% polyvinyl alcohol or the ethanolic solution of polyvinyl butyral resin that binding agent is preferably mass fraction, under 200MPa to 300MPa forcing press, be pressed into sheet, at 900 ℃ to 1200 ℃, sintering makes solid electrolyte target material;
(3) porous ceramic substrate plated film: take porous ceramic as film forming substrate, the middle solid electrolyte target material of preparing of the step (2) of take is target, the method that adopts magnetron sputtering, by evenly plating the film of one deck solid electrolyte on porous ceramic, makes described solid electrolyte membrane.
Described solid electrolyte film thickness is generally less than 10 microns, take that to cover porous ceramic substrate one side be completely standard, and film thickness is adjusted by controlling the magnetron sputtering time.Described solid electrolyte membrane, is guaranteeing that under uniform condition, thinner its resistance is lower, and performance is better.
Distance during sputter coating between target and chip bench is preferably 10 to 15cm, sputter coating is that the angle of target and chip bench is 30 ° to 45 °, during sputter coating, argon pressure is 0.5 to 2Pa in vacuum chamber, and during sputter coating, radio-frequency power supply power is 50W to 200W.
Solid electrolyte membrane provided by the invention, can be applicable to the preparation of lithium-air battery.
A lithium-air battery, as shown in Figure 2, comprises lithium anode, solid electrolyte membrane, electrolyte and porous anode; The porous ceramic layer of described solid electrolyte membrane, is full of electrolyte in its hole; Described solid electrolyte membrane is arranged between lithium anode and porous anode, isolates described lithium anode and porous anode.Preferably, described lithium anode is arranged on how empty ceramic layer one side of described solid electrolyte membrane, and described porous anode is arranged on described solid-state electrolyte layer one side.
Be below embodiment:
Embodiment 1
A solid electrolyte membrane, comprises solid-state electrolyte layer and porous ceramic layer, and described solid electrolyte layer thickness is at 1.8 microns, and the flexural strength of described porous ceramic layer is 100N/mm
2, its lithium ion conductivity is 6.0 * 10
-5siemens/cm, described porous ceramic layer thickness is 170 microns, described solid-state electrolyte layer uniform fold is on porous ceramic layer.
The material of described solid-state electrolyte layer is Ca-Ti ore type lithium ion conductor Li
3xla
(2/3)-xtiO
3(x=0.1, i.e. Li
0.3la
0.57tiO
3, hereinafter to be referred as LLTO).
Described porous ceramic layer is bilateral anodised aluminium.
Described solid electrolyte membrane, its preparation method, comprises the following steps:
(1) preparation of solid electrolyte presoma: press chemical formula Li
3xla
(2/3)-xtiO
3(x=0.1) (be Li
0.3la
0.57tiO
3) in the stoichiometric proportion 0.3:0.57:1 of Li, La, Ti, choose Li
2cO
3, La
2o
3, TiO
2as raw material, Li wherein
2cO
3excessive 5% (mass fraction), in anhydrous ethanol medium with 6 hours post-dryings of speed ball milling of 180r/min, make the mixed uniformly powder of described raw material, described powder is calcined 10 hours in 600 ℃ of air, make described solid electrolyte precursor powder.
(2) preparation of solid electrolyte target material: will add the binder solution of its quality 1% in the solid electrolyte precursor powder making in step (1), described binder solution is that mass fraction is the ethanolic solution of 5% polyvinyl alcohol, under 200MPa forcing press, be pressed into sheet, at 1000 ℃, calcine 5 hours, heating rate is 3 ℃/min, makes solid electrolyte target material;
(3) porous ceramic substrate plated film: take diameter as 25mm, thickness is 170 μ m, pore size is that the bilateral anodised aluminium potsherd of 200nm to 300nm is film forming substrate, the middle solid electrolyte target material of preparing of the step (2) of take is target, adopt the method for magnetron sputtering, on bilateral anodised aluminium, evenly plate the film of one deck solid electrolyte, make described solid electrolyte membrane.
Distance during sputter coating between target and chip bench is 10cm, and sputter coating is that the angle of target and chip bench is 35 °, and during sputter coating, in vacuum chamber, argon pressure is 1Pa, and during sputter coating, radio-frequency power supply power is 150W, and the plated film time is 8 hours.
Described solid electrolyte membrane, can be applicable to the preparation of lithium-air battery.
A lithium-air battery, comprises lithium anode, described solid electrolyte membrane, electrolyte and porous anode; The porous ceramic layer of described solid electrolyte membrane, is full of electrolyte in its hole; Described solid electrolyte membrane is arranged between lithium anode and porous anode, isolates described lithium anode and porous anode.Described lithium anode is arranged on how empty ceramic layer one side of described solid electrolyte membrane, and described porous anode is arranged on described solid-state electrolyte layer one side.Be prepared as follows:
In the glove box of argon gas atmosphere, with the lithium sheet that described solid electrolyte membrane and Copper Foil are 0.5mm by thickness, encapsulate, lithium sheet contacts with described solid electrolyte membrane porous ceramic layer, and infiltrates at 1mol/L lithium hexafluoro phosphate (LiPF
6in)-propene carbonate (PC) electrolyte, meanwhile, by one little nickel foam, guarantee contacting of lithium sheet and Copper Foil, with the UV-cured resin edge sealing of electrolyte resistance corrosion, guarantee that negative pole seals.After negative pole has sealed, shift out glove box, in described solid electrolyte membrane solid-state electrolyte layer one side, the graphene sponge of placing porous, and with the phosphoric acid (H of 0.1mol/L
3pO
4)-1M lithium dihydrogen phosphate (LiH
2pO
4) solution immersion graphene sponge, by a small pieces nickel foam, as plus plate current-collecting body, so just formed a mixed electrolyte lithium-air battery, can simply be expressed as (-) Li|LiPF
6-PC|LLTO@AAO|H
3pO
4-LiH
2pO
4| Graphene (+), in air, after standing 1 hour, to discharge, current density is 0.2mA/cm
2time, cell voltage is 3.62V, and total cell weight is 0.38g (weighing before electric discharge), and discharge capacity of the cell is 46mAh.
Embodiment 2
A solid electrolyte membrane, comprises solid-state electrolyte layer and porous ceramic layer, and described solid electrolyte layer thickness is at 1 micron, and the flexural strength of described porous ceramic layer is at 100N/mm
2, its lithium ion conductivity is 1.2 * 10
-6siemens/cm, described porous ceramic layer thickness is 170 microns, described solid-state electrolyte layer uniform fold is on porous ceramic layer.
The material of described solid-state electrolyte layer is, NASICON type lithium ion conductor Li
1+yge
2-x-yti
xal
y(PO
4)
3(x=0.3 wherein, y=0.21, i.e. Li
1.21ge
1.49al
0.21ti
0.3(PO
4)
3, hereinafter to be referred as LGATP).
Described porous ceramic layer is bilateral anodised aluminium.
Described solid electrolyte membrane, its preparation method, comprises the following steps:
(1) preparation of solid electrolyte presoma: press chemical formula Li
1.21ge
1.49al
0.21ti
0.3(PO
4)
3middle Li, Ge, Al, Ti, PO
4stoichiometric proportion 1.21:1.49:0.21:0.3:3, choose Li
2cO
3, GeO
2, Al
2o
3, TiO
2and NH4H
2pO
4as raw material, Li wherein
2cO
3excessive 5% (mass fraction) with 6 hours post-dryings of speed ball milling of 180r/min, makes the mixed uniformly powder of described raw material in anhydrous ethanol medium, by 500 ℃, described powder, calcines 10 hours, makes described solid electrolyte precursor powder.
(2) preparation of solid electrolyte target material: will add the binder solution of its quality 10% in the solid electrolyte precursor powder making in step (1), described binder solution is the ethanolic solution of the polyvinyl butyral resin of mass fraction 1%, under 200MPa forcing press, be pressed into sheet, at 900 ℃, calcine 5 hours, heating rate is 3 ℃/min, makes solid electrolyte target material;
(3) porous ceramic substrate plated film: take diameter as 25mm, thickness is 170 μ m, pore size is that the bilateral anodised aluminium potsherd of 200-300nm is film forming substrate, the middle solid electrolyte target material of preparing of the step (2) of take is target, adopt the method for magnetron sputtering, on bilateral anodised aluminium, evenly plate the film of one deck solid electrolyte, make described solid electrolyte membrane.
Distance during sputter coating between target and chip bench is 10cm, and sputter coating is that the angle of target and chip bench is 35 °, and during sputter coating, in vacuum chamber, argon pressure is 2Pa, and during sputter coating, radio-frequency power supply power is 100W, and the plated film time is 10 hours.
Solid electrolyte membrane provided by the invention, can be applicable to the preparation of lithium-air battery.
A lithium-air battery, comprises lithium anode, described solid electrolyte membrane, electrolyte and porous anode; The porous ceramic layer of described solid electrolyte membrane, is full of electrolyte in its hole; Described solid electrolyte membrane is arranged between lithium anode and porous anode, isolates described lithium anode and porous anode.Described lithium anode is arranged on how empty ceramic layer one side of described solid electrolyte membrane, and described porous anode is arranged on described solid-state electrolyte layer one side.Be prepared as follows:
In the glove box of argon gas atmosphere, with the lithium sheet that described solid electrolyte membrane and Copper Foil are 0.5mm by thickness, encapsulate, lithium sheet contacts with described solid electrolyte membrane porous ceramic layer, and infiltrates at 1mol/L lithium hexafluoro phosphate (LiPF
6in)-propene carbonate (PC) electrolyte, meanwhile, by one little nickel foam, guarantee contacting of lithium sheet and Copper Foil, with the UV-cured resin edge sealing of electrolyte resistance corrosion, guarantee that negative pole seals.After negative pole has sealed, shift out glove box, in described solid electrolyte membrane solid-state electrolyte layer one side, the graphene sponge of placing porous, and with 1mol/L lithium chloride (LiCl) solution immersion graphene sponge, by a small pieces nickel foam, as plus plate current-collecting body, so just form a mixed electrolyte lithium-air battery, can simply be expressed as (-) Li|LiPF
6-PC|LGATP AAO|LiCl| Graphene (+) discharges after standing 1 hour in air, and when current density is 0.05mA/cm2, cell voltage is 3.64V, and total cell weight is 0.45g (weighing before electric discharge), and discharge capacity of the cell is 39mAh.
Embodiment 3
A solid electrolyte membrane, comprises solid-state electrolyte layer and porous ceramic layer, and described solid electrolyte layer thickness is at 10 microns, and the flexural strength of described porous ceramic layer is at 170N/mm
2, its lithium ion conductivity is 5.2 * 10
-5siemens/cm, described porous ceramic layer thickness is 300 microns, described solid-state electrolyte layer uniform fold is on porous ceramic layer.
The material of described solid-state electrolyte layer is LISICON type lithium ion conductor Li
14znGe
4o
16(hereinafter to be referred as LZGO).
Described porous ceramic layer is the porous oxidation zircon ceramic that utilizes pore creating material to obtain.
Described solid electrolyte membrane, its preparation method, comprises the following steps:
(1) preparation of solid electrolyte presoma: press chemical formula Li
14znGe
4o
16the stoichiometric proportion 14:1:4 of middle Li, Zn, Ge, chooses Li
2cO
3, ZnO, GeO
2as raw material, Li wherein
2cO
3excessive 5% (mass fraction), in anhydrous ethanol medium with 6 hours post-dryings of speed ball milling of 180r/min, make the mixed uniformly powder of described raw material, described powder is calcined 10 hours in 650 ℃ of air, make described solid electrolyte precursor powder.
(2) preparation of solid electrolyte target material: will add the binder solution of its quality 4% in the solid electrolyte precursor powder making in step (1), described binder solution is the ethanolic solution of the polyvinyl butyral resin of mass fraction 3%, under 300MPa forcing press, be pressed into sheet, at 1100 ℃, calcine 5 hours, heating rate is 3 ℃/min, makes solid electrolyte target material;
(3) porous ceramic substrate plated film: take diameter as 25mm, thickness is 300 microns, pore size is that the porous oxidation zircon ceramic of 1.5 microns is film forming substrate, the middle solid electrolyte target material of preparing of the step (2) of take is target, adopt the method for magnetron sputtering, on bilateral anodised aluminium, evenly plate the film of one deck solid electrolyte, make described solid electrolyte membrane.
Distance during sputter coating between target and chip bench is 10cm, and sputter coating is that the angle of target and chip bench is 35 °, and during sputter coating, in vacuum chamber, argon pressure is 1Pa, and during sputter coating, radio-frequency power supply power is 200W, and the plated film time is 20 hours.
Solid electrolyte membrane provided by the invention, can be applicable to the preparation of lithium-air battery.
A lithium-air battery, comprises lithium anode, described solid electrolyte membrane, electrolyte and porous anode; The porous ceramic layer of described solid electrolyte membrane, is full of electrolyte in its hole; Described solid electrolyte membrane is arranged between lithium anode and porous anode, isolates described lithium anode and porous anode.Described lithium anode is arranged on how empty ceramic layer one side of described solid electrolyte membrane, and described porous anode is arranged on described solid-state electrolyte layer one side.Be prepared as follows:
In the glove box of argon gas atmosphere, with the lithium sheet that described solid electrolyte membrane and Copper Foil are 0.5mm by thickness, encapsulate, lithium sheet contacts with described solid electrolyte membrane porous ceramic layer, and infiltrates at 1mol/L lithium hexafluoro phosphate (LiPF
6in)-propene carbonate (PC) electrolyte, meanwhile, by one little nickel foam, guarantee contacting of lithium sheet and Copper Foil, with the UV-cured resin edge sealing of electrolyte resistance corrosion, guarantee that negative pole seals.After negative pole has sealed, shift out glove box, in described solid electrolyte membrane solid-state electrolyte layer one side, the graphene sponge of placing porous, and with the phosphoric acid (H of 0.1mol/L
3pO
4)-1M lithium dihydrogen phosphate (LiH
2pO
4) solution immersion graphene sponge, by a small pieces nickel foam, as plus plate current-collecting body, so just formed a mixed electrolyte lithium-air battery, can simply be expressed as (-) Li|LiPF
6-PC|LZGO@ZrO
2| H
3pO
4-LiH
2pO
4| Graphene (+), in air, after standing 1 hour, to discharge, current density is 0.05mA/cm
2time, cell voltage is 3.45V, and total cell weight is 0.45g (weighing before electric discharge), and discharge capacity of the cell is 15mAh.
Embodiment 4
A solid electrolyte membrane, comprises solid-state electrolyte layer and porous ceramic layer, and described solid electrolyte layer thickness is at 0.5 micron, and the flexural strength of described porous ceramic layer is at 80N/mm
2, its lithium ion conductivity is 2.6 * 10
-5siemens/cm, described porous ceramic layer thickness is 100 microns, described solid-state electrolyte layer uniform fold is on porous ceramic layer.
The material of described solid-state electrolyte layer is carbuncle type lithium ion conductor Li
5la
3ta
2o
12(hereinafter to be referred as LLTAO).
Described porous ceramic layer is the ceramic super-filtering film of gradient pore-size distribution.
Described solid electrolyte membrane, its preparation method, comprises the following steps:
(1) preparation of solid electrolyte presoma: press chemical formula Li
5la
3ta
2o
12the stoichiometric proportion 5:3:2 of middle Li, La, Ta, chooses Li
2cO
3, La
2o
3, Ta
2o
5as raw material, Li wherein
2cO
3excessive 5% (mass fraction), in anhydrous ethanol medium with 6 hours post-dryings of speed ball milling of 180r/min, make the mixed uniformly powder of described raw material, described powder is calcined 10 hours in 700 ℃ of air, make described solid electrolyte precursor powder.
(2) preparation of solid electrolyte target material: will add the binder solution of its quality 4% in the solid electrolyte precursor powder making in step (1), described binder solution is the ethanolic solution of the polyvinyl butyral resin of mass fraction 3%, under 250MPa forcing press, be pressed into sheet, at 1200 ℃, calcine 5 hours, heating rate is 3 ℃/min, makes solid electrolyte target material;
(3) porous ceramic substrate plated film: take diameter as 25mm, thickness is 150 μ m, pore-size distribution is that the ceramic super-filtering film of 2-50nm is film forming substrate, a little side plated film in aperture, the middle solid electrolyte target material of preparing of the step (2) of take is target, adopt the method for magnetron sputtering, on bilateral anodised aluminium, evenly plate the film of one deck solid electrolyte, make described solid electrolyte membrane.
Distance during sputter coating between target and chip bench is 10cm, and sputter coating is that the angle of target and chip bench is 35 °, and during sputter coating, in vacuum chamber, argon pressure is 1Pa, and during sputter coating, radio-frequency power supply power is 60W, and the plated film time is 2 hours.
Solid electrolyte membrane provided by the invention, can be applicable to the preparation of lithium-air battery.
A lithium-air battery, comprises lithium anode, described solid electrolyte membrane, electrolyte and porous anode; The porous ceramic layer of described solid electrolyte membrane, is full of electrolyte in its hole; Described solid electrolyte membrane is arranged between lithium anode and porous anode, isolates described lithium anode and porous anode.Described lithium anode is arranged on how empty ceramic layer one side of described solid electrolyte membrane, and described porous anode is arranged on described solid-state electrolyte layer one side.Be prepared as follows:
In the glove box of argon gas atmosphere, with the lithium sheet that described solid electrolyte membrane and Copper Foil are 0.5mm by thickness, encapsulate, lithium sheet contacts with described solid electrolyte membrane porous ceramic layer, and infiltrates at 1mol/L lithium hexafluoro phosphate (LiPF
6in)-propene carbonate (PC) electrolyte, meanwhile, by one little nickel foam, guarantee contacting of lithium sheet and Copper Foil, with the UV-cured resin edge sealing of electrolyte resistance corrosion, guarantee that negative pole seals.After negative pole has sealed, shift out glove box, in described solid electrolyte membrane solid-state electrolyte layer one side, the graphene sponge of placing porous, and with lithium chloride (LiCl) the solution immersion graphene sponge of 1mol/L, by a small pieces nickel foam, as plus plate current-collecting body, so just form a mixed electrolyte lithium-air battery, can simply be expressed as (-) Li|LiPF
6-PC|LLTAO milipore filter | LiCl| Graphene (+), in air, after standing 1 hour, to discharge, current density is 0.02mA/cm
2time, cell voltage is 3.54V, and total cell weight is 0.45g (weighing before electric discharge), and discharge capacity of the cell is 9mAh.
Embodiment 5
A solid electrolyte membrane, comprises solid-state electrolyte layer and porous ceramic layer, and described solid electrolyte layer thickness is at 0.5 micron, and the flexural strength of described porous ceramic layer is at 110N/mm
2, its lithium ion conductivity is 5.8 * 10
-5siemens/cm, described porous ceramic layer thickness is 260 microns, described solid-state electrolyte layer uniform fold is on porous ceramic layer.
The material of described solid-state electrolyte layer is Ca-Ti ore type lithium ion conductor Li
3xla
(2/3)-xtiO
3(x=0.1, i.e. Li
0.3la
0.57tiO
3, hereinafter to be referred as LLTO).
Described porous ceramic layer is the potsherd that mesoporous silica gel is pressed into.
Described solid electrolyte membrane, its preparation method, comprises the following steps:
(1) preparation of solid electrolyte presoma: press chemical formula Li
3xla
(2/3)-xtiO
3(x=0.1) (be Li
0.3la
0.57tiO
3) in the stoichiometric proportion 0.3:0.57:1 of Li, La, Ti, choose Li
2cO
3, La
2o
3, TiO
2as raw material, Li wherein
2cO
3excessive 5% (mass fraction), in anhydrous ethanol medium with 6 hours post-dryings of speed ball milling of 180r/min, make the mixed uniformly powder of described raw material, described powder is calcined 10 hours in 600 ℃ of air, make described solid electrolyte precursor powder.
(2) preparation of solid electrolyte target material: will add the binder solution of its quality 1% in the solid electrolyte precursor powder making in step (1), described binder solution is that mass fraction is the ethanolic solution of 5% polyvinyl alcohol, under 200MPa forcing press, be pressed into sheet, at 1000 ℃, calcine 5 hours, heating rate is 3 ℃/min, makes solid electrolyte target material;
(3) porous ceramic substrate plated film: take diameter as 20mm, thickness is 260 μ m, pore size is that the mesoporous silica gel potsherd of 25nm left and right is film forming substrate, the middle solid electrolyte target material of preparing of the step (2) of take is target, adopt the method for magnetron sputtering, on bilateral anodised aluminium, evenly plate the film of one deck solid electrolyte, make described solid electrolyte membrane.
Distance during sputter coating between target and chip bench is 10cm, and sputter coating is that the angle of target and chip bench is 35 °, and during sputter coating, in vacuum chamber, argon pressure is 1Pa, and during sputter coating, radio-frequency power supply power is 80W, and the plated film time is 5 hours.
Solid electrolyte membrane provided by the invention, can be applicable to the preparation of lithium-air battery.
A lithium-air battery, comprises lithium anode, described solid electrolyte membrane, electrolyte and porous anode; The porous ceramic layer of described solid electrolyte membrane, is full of electrolyte in its hole; Described solid electrolyte membrane is arranged between lithium anode and porous anode, isolates described lithium anode and porous anode.Described lithium anode is arranged on how empty ceramic layer one side of described solid electrolyte membrane, and described porous anode is arranged on described solid-state electrolyte layer one side.Be prepared as follows:
In the glove box of argon gas atmosphere, with the lithium sheet that described solid electrolyte membrane and Copper Foil are 0.5mm by thickness, encapsulate, lithium sheet contacts with described solid electrolyte membrane porous ceramic layer, and infiltrates at 1mol/L lithium hexafluoro phosphate (LiPF
6in)-propene carbonate (PC) electrolyte, meanwhile, by one little nickel foam, guarantee contacting of lithium sheet and Copper Foil, with the UV-cured resin edge sealing of electrolyte resistance corrosion, guarantee that negative pole seals.After negative pole has sealed, shift out glove box, in described solid electrolyte membrane solid-state electrolyte layer one side, the graphene sponge of placing porous, and with lithium chloride (LiCl) the solution immersion graphene sponge of 1mol/L, by a small pieces nickel foam, as plus plate current-collecting body, so just form a mixed electrolyte lithium-air battery, can simply be expressed as (-) Li|LiPF
6-PC|LLTO mesoporous silica gel | LiCl| Graphene (+), in air, after standing 1 hour, to discharge, current density is 0.02mA/cm
2time, cell voltage is 3.49V, and total cell weight is 0.45g (weighing before electric discharge), and discharge capacity of the cell is 11mAh.
Those skilled in the art will readily understand; the foregoing is only preferred embodiment of the present invention; not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
1. a solid electrolyte membrane, it is characterized in that, comprise solid-state electrolyte layer and porous ceramic layer, described solid electrolyte layer thickness is between 0.5 micron to 10 microns, described porous ceramic layer thickness is between 100 microns to 300 microns, and described solid-state electrolyte layer uniform fold is on porous ceramic layer.
2. solid electrolyte membrane as claimed in claim 1, is characterized in that, the conductivity at room temperature of described solid-state electrolyte layer is 10
-5to 10
-6siemens/cm.
3. solid electrolyte membrane as claimed in claim 2, is characterized in that, the material of described solid-state electrolyte layer is NASICON type lithium ion conductor Li
1+xti
2-xm
x(PO
4)
3, Li
1+xge
2-xm
x(PO
4)
3(0.1<x<0.7, M=Al, Ga, In, Sc), Ca-Ti ore type lithium ion conductor Li
3xla
(2/3)-xtiO
3(0<x<0.16), LISICON type lithium ion conductor Li
14znGe
4o
16or carbuncle type lithium ion conductor Li
5la
3m
2o
12(M=Ta, Nb).
4. solid electrolyte membrane as claimed in claim 1, is characterized in that, the flexural strength of described porous ceramic layer is at 80N/mm
2to 170N/mm
2between.
5. solid electrolyte membrane as claimed in claim 4, is characterized in that, described porous ceramic layer is the ceramic super-filtering film of the porous oxidation zircon ceramic, mesoporous silica gel, bilateral anodised aluminium or the gradient pore-size distribution that utilize pore creating material to obtain.
6. the preparation method of the solid electrolyte membrane as described in claim 1 to 5 any one, is characterized in that, comprises the following steps:
(1) preparation of solid electrolyte presoma: the raw material of respective element is dispersed in organic solvent according to the element ratio of target solid electrolyte, oven dry makes the mixed uniformly powder of described raw material, and described powder sintering at 500 ℃ to 700 ℃ is made to described solid electrolyte precursor powder;
(2) preparation of solid electrolyte target material: the binding agent that the solid electrolyte precursor powder making in step (1) is added to its quality 1% to 10%, under 200MPa to 300MPa forcing press, be pressed into sheet, at 900 ℃ to 1200 ℃, sintering makes solid electrolyte target material;
(3) porous ceramic substrate plated film: take porous ceramic as film forming substrate, the middle solid electrolyte target material of preparing of the step (2) of take is target, the method that adopts magnetron sputtering, by evenly plating the film of one deck solid electrolyte on porous ceramic, makes described solid electrolyte membrane.
7. preparation method as claimed in claim 6, is characterized in that, oxide, carbonate compound and/or phosphate compounds that the described raw material of step (1) is respective element.
8. preparation method as claimed in claim 6, is characterized in that, the described binding agent of step (2) is the polyvinyl alcohol of mass fraction 1% to 5% or the ethanolic solution of polyvinyl butyral resin.
9. the solid electrolyte membrane as described in claim 1 to 5 any one, is applied to the preparation of lithium-air battery.
10. a lithium-air battery for application solid electrolyte membrane as described in claim 1 to 5 any one, is characterized in that, comprises lithium anode, the solid electrolyte membrane as described in claim 1 to 5, electrolyte and porous anode; The porous ceramic layer of described solid electrolyte membrane, is full of electrolyte in its hole; Described solid electrolyte membrane is arranged between lithium anode and porous anode, isolates described lithium anode and porous anode.
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