CN105742761B - A kind of full-solid lithium air battery and preparation method and application - Google Patents
A kind of full-solid lithium air battery and preparation method and application Download PDFInfo
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- CN105742761B CN105742761B CN201610112823.2A CN201610112823A CN105742761B CN 105742761 B CN105742761 B CN 105742761B CN 201610112823 A CN201610112823 A CN 201610112823A CN 105742761 B CN105742761 B CN 105742761B
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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
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
Abstract
The invention discloses a kind of full-solid lithium air battery and preparation method and application.Full-solid lithium air battery provided by the invention includes lithium anodes, porous ceramic support, thin dense electrolyte film, porous cathode film, encapsulant, current collector and lead；Use carbuncle type lithium ion solid electrolyte material to make porous supporting body, in air electrode catalyst and lithium anodes permeability hole, expanded cell reaction three phase boundary, reduce battery polarization resistance；Cell electrolyte film thickness is less than 30 μm, shortens lithium ion transport path, reduces battery Ohmic resistance；Battery is the tubular structure of one end closing, and lithium anodes are poured in pipe, and cell sealing is simple, is easy to be operated at different conditions.Full-solid lithium air battery prepared by the present invention has the advantages that charge/discharge capacity height, good rate capability, cyclical stability are high, operating temperature range is wide, suitable for various mobile electronic devices and electrokinetic cell field.
Description
Technical field
The present invention relates to a kind of lithium-air battery, and in particular to a kind of all solid state lithium-air battery and preparation method thereof with
Using belonging to high performance chemical electric power source field.
Background technology
At present, the power resources of small and medium-sized car are mainly the burning of bavin gasoline, however as the increasingly withered of petroleum resources
The worsening with environmental problem is exhausted, people substitute there is an urgent need to find a kind of green energy resource.In green energy resources numerous at present
In substitute, lithium ion battery is with of a relatively high energy density, good high rate performance and cyclical stability, memory-less effect
The features such as, instead of plumbic acid, NI-G, Ni-MH battery recent years rapidly turns into the most popular high-energy power of electric car in the market
Battery.
Lithium-air battery is a kind of battery using oxygen as positive electrode active materials, using lithium metal as negative active core-shell material, by
Inside battery need not be stored in oxygen, its theoretical energy density is up to 5.21 kWh/kg (oxygenous) or 11.14 kWh/
Kg (not oxygenous), far above the theoretical energy density of conventional lithium ion battery（200-250 Wh/kg）, its performance can be with gasoline
(12.22 kWh/kg) compares favourably, and therefore, lithium-air battery is also referred to as lithium battery of future generation or ultimate battery.Lithium-air electricity
During tank discharge, the oxygen molecule in air is transformed into negative oxygen ion under catalyst action or crosses negative oxygen ion, and is passed with anode
The lithium ion passed combines generation oxidate for lithium or lithium peroxide；During electric discharge, the oxidate for lithium or lithium peroxide of generation
Compound is decomposed again, generates oxygen and lithium metal, realizes the Reversible Cycle put and filled；This is empty with aluminium-air cell, the zinc of routine
The metal-air batteries such as pneumoelectric pond have very greatly not, and aluminium air and zinc-air battery mainly work in alkaline solution, mainly do one
Primary cell uses.
Lithium-air battery has as high-energy-density power supply of new generation in the field such as portable type electronic product and communication apparatus
Have broad application prospects, can especially meet the requirement of the high-energy-density of electric car power supply.In the prior art, lithium-air
Battery research is more based on existing lithium ion battery, using organic carbonate lipid electrolyte as organic electrolyte solution, but
Organic electrolyte is inflammable and explosive, and this battery explosion, fire for causing electrolyte leakage and thus triggering happen occasionally.Improve
The safety in utilization of lithium-air battery, most directly, most efficient method be exactly that not use inflammable and explosive organic bath molten
Liquid, using non-ignitable not quick-fried all solid state lithium ion electrolyte, the simplification of battery safety device can be both realized, can significantly be dropped again
Low battery manufacture cost.
Prior art reports a kind of solid-state lithium-air battery based on phosphoric acid salt solid electrolyte, but all uses
Phosphoric acid salt solid electrolyte material with NASICON structures, such as Li1.3Al0.3Ti1.7(PO4)3And Li (LATP)1+ xAlyGe2-x(PO4)3(LAGP), this kind of solid electrolyte material is unstable, is easily reacted with lithium anodes；Therefore, exist
In these solid-state lithium-air batteries reported, also need to place to satisfy between lithium anodes and solid electrolyte to be soaked with liquid
The diaphragm material of organic electrolyte, lithium ion transport path when this aspect adds battery work, on the other hand, organic electrolysis
The use of liquid, still inevitably brings the safety issue of battery, and battery can not be referred to as all solid state lithium-air battery.
Carbuncle type oxide lithium ion solid electrolyte has higher lithium ion conductive, can improve its conductance by doping
And sintering character；But it is concentrated mainly on material system on carbuncle type oxide lithium ion solid state electrolysis Quality Research at present
Standby, basic performance improvement and lithium ion pass through mechanism etc., do not have also on making all solid state lithium-air battery device using it
Have been reported.In addition, existing solid-state lithium-air battery is all button-shaped, lithium anodes, air electrode and solid state electrolysis
Purely it is the physical contact realized by extruding between matter, the cell contact resistance that this mode assembles is larger, and during cell reaction
Lithium ion and negative oxygen ion are only also larger in layer and layer contact surface transmission, battery polarization resistance.
The content of the invention
It is an object of the invention to provide a kind of all solid state lithium-air battery and preparation method thereof, carbuncle type is utilized first
Oxide is as lithium ion solid electrolyte, by between lithium anodes, air electrode and lithium ion solid electrolyte
Contact interface regulates and controls through row and optimization, improves all solid state lithium-air battery charge/discharge capacity, forthright again and stability；So as to true
Positive obtains a kind of all solid state lithium-air battery, has charge/discharge capacity height, good rate capability, cyclical stability height, work temperature
The advantages that scope is wide is spent, suitable for various mobile electronic devices and electrokinetic cell field.
To achieve the above object of the invention, the technical solution adopted by the present invention is：
A kind of all solid state lithium-air battery, including it is lithium anodes, porous ceramic support, thin dense electrolyte film, more
Hole cathode thin film, encapsulant, current collector, galvanic anode lead and cell cathode lead；The porous cathode film
Including stephanoporate framework and the cathod catalyst being carried on stephanoporate framework；The porous ceramic support is the pipe of one end closing
Formula structure；The lithium anodes are located in the inner chamber and hole of porous ceramic support；The thin dense electrolyte film is located at
Porous ceramic support lateral wall；The porous cathode film is located at thin dense electrolyte film lateral wall；The sealing material material position
In one end of porous ceramic support opening；The material of the porous ceramic support is carbuncle type lithium ion solid electrolyte
Material；The material of the thin dense electrolyte film is carbuncle type lithium ion solid electrolyte material.
The porous ceramic support of the present invention is porous lithium ion solid electrolyte ceramic, and structure is the tubular type of one end closing
Structure, another end opening, the part of side wall parcel is inner chamber, and lithium anodes are uniformly poured into the tubular structure of one end closing
In inner chamber, and fill the hole connected on porous ceramic support wall with inner chamber；In porous ceramic support, radially, by
From inside to outside, the diameter in hole tapers into, and changes in gradient, and the direction in hole is consistent with active material transmission direction, and macropore is advantageous to
Mass transfer, small pore specific surface area is big, is advantageous to increase electrochemical reaction effective area, so as to improve the performance of battery；It is porous
The distance between cathode thin film and porous ceramic support edge of opening are 3~10mm, porous cathode film end and porous pottery
There is a certain distance porcelain supporter openend, to avoid negative electrode and anode in electrolytic tube opening short circuit；Utilize waterproof sealing
Material is to porous ceramic support opening（Battery openend）Sealed.Current collector, galvanic anode lead and battery
The connection of cathode leg is lithium-air battery conventional arrangement.
The invention also discloses the preparation method of above-mentioned all solid state lithium-air battery, comprise the following steps：
（1）In the presence of consisting of phase-transferring agent, using carbuncle type lithium ion solid electrolyte material as raw material, porous ceramics is prepared
Supporter green compact；Then green compact are sintered 12~24 hours in 1000~1100 DEG C, obtains porous ceramic support；
（2）In the presence of organic additive, carbuncle type lithium ion solid electrolyte material is scattered in organic solvent,
Obtain dipping sizing agent；Then by step（1）Porous ceramic support be impregnated in the dipping sizing agent；After the completion of dipping, in
1000~1250 DEG C sinter 8~12 hours, i.e., form thin dense electrolyte film in porous ceramic support lateral wall；
（3）The raw material for preparing cathod catalyst is added to the water, is configured to cathod catalyst precursor solution；By garnet
Type lithium ion solid electrolyte material, bonding agent and pore creating material mixing, prepare and apply slurry；Then slurry will be applied to be painted on
Step（2）Obtained thin dense electrolyte film surface；After the completion of brushing, sinter 4~8 hours, that is, causing in 1000~1100 DEG C
Close electrolyte membrane surface forms stephanoporate framework；By stephanoporate framework and cathod catalyst precursor solution it is compound after, by calcining,
So that cathod catalyst is carried on stephanoporate framework；
（4）By lithium metal liquation implantation step（3）Porous ceramic support inner chamber in, then galvanic anode lead is inserted
Enter in lithium metal liquation；After lithium metal solidification, encapsulant is set in porous ceramic support open at one end；Then will with silver paste
Cell cathode lead is Nian Jie with stephanoporate framework；Obtain all solid lithium-air cell.
In the present invention, carbuncle type lithium ion solid electrolyte material is Li7La3Zr2O12Or Li7La3Zr2-xMxO12,
Wherein M is Ta, Nb, Sb, Bi, Ti, Y or Al；Galvanic anode lead is silver wire, cell cathode lead is silver wire；Encapsulant
For paraffin or bicomponent epoxy resin adhesive；Cathod catalyst is spinel oxide or perovskite oxide, such as
AB2O4Spinel oxide is NiCo2O4、CoFe2O4、MnCo2O4And CuCo2O4, ABO3Perovskite is oxidized to
Ba0.9Co0.7Fe0.2Nb0.1O3、La0.8Sr0.2MnO3、Ba0.5Sr0.5Co0.8Fe0.2O3Deng.
In above-mentioned technical proposal, using carbuncle type lithium ion solid electrolyte material as raw material, by consisting of phase-transferring agent and pomegranate
Ground after the mixing of stone-type lithium ion solid electrolyte material uniformly, it is more that the tubular structure closed one end is prepared using phase-inversion technologies
Hole ceramic supporting body green compact, after then sintered, obtained porous ceramic support thickness of pipe wall is the mm of 0.5 mm~3, draw ratio
For（0.06~0.5）: 1, for example external diameter is 0.6~1.5 cm, the cm of length 3~10, and along pipe radial direction from inside to outside, hole
In finger, from large to small.Consisting of phase-transferring agent is polyether sulfone powder, can use N, N- dimethyl pyrrolidones are as solvent；
The mass ratio of consisting of phase-transferring agent and carbuncle type lithium ion solid electrolyte material is 0.8~1.2: 1.According to the implementation of the present invention
Example, carbuncle type lithium ion solid electrolyte material powder, consisting of phase-transferring agent is uniform in ball grinder, adding solvent grinding, obtain
Obtain slurry；Above-mentioned slurry is impregnated using glass bar, is quickly put into pure water after rotation uniformly, static half an hour, slowly extracts
Glass bar just obtains the tubular type green compact of one end closing, then sinters, obtains tubular porous supporter, the caliber and length of supporter
It can be regulated and controled according to the number of the diameter using glass bar and slurry；Slurry can also be set by existing injection moulding
Prepare standby green compact.
In above-mentioned technical proposal, fine and close electrolytic thin-membrane is prepared using infusion process, in the presence of organic additive, by stone
Garnet type lithium ion solid electrolyte material is scattered in organic solvent, ball milling 3~5 hours, obtains dipping sizing agent；Porous ceramics
The number that supporter is impregnated in the dipping sizing agent is 2~6 times, dries after dipping impregnated next time again every time；It is organic
Additive is the one or more in triethanolamine, dibutyl phthalate, polyethylene glycol, polyvinyl butyral resin；It is organic
Solvent is alcoholic solvent；The dosage of organic additive is the 14%~15% of carbuncle type lithium ion solid electrolyte material quality；
Thickness to thin dense electrolyte film is 2~30 μm, can be adjusted by dipping time.
In above-mentioned technical proposal, pore creating material is activated carbon such as graphite, or starch；The dosage of pore creating material is carbuncle type
The 40~100% of lithium ion solid electrolyte material quality, using brushing method fine and close solid electrolyte surface make porous lithium from
Sub- solid electrolyte skeleton, bone porous porosity is obtained as 50~80%；Stephanoporate framework and cathod catalyst precursor solution
Compound mode is that will be dripped in stephanoporate framework impregnated cathode Catalyst precursor solutions or by cathod catalyst precursor solution
In on stephanoporate framework；Calcining heat is 380~650 DEG C, and the time is 2~8 hours.Cathod catalyst presoma the moon as needed
Electrode catalyst（AB2O4Spinel oxide and ABO3Perovskite oxidation etc.）Prepare, can repeatedly be impregnated or repeatedly dripped
Add, to cause catalyst to be grown in stephanoporate framework uniformly.The stephanoporate framework for loading cathod catalyst forms porous cathode film,
Thickness is 30~150 μm；Air electrode current collector and lead are made using silver paste and filamentary silver.
In above-mentioned technical proposal, in the glove box full of high-purity argon gas（Oxygen and water vapour content are less than 1ppm）By gold
Belong to lithium fusing, and molten metal lithium is filling in porous ceramic support inner chamber, galvanic anode lead is then inserted into gold
Belong in lithium；20~40 minutes are incubated in 185 DEG C, ensures that molten metal lithium fully infiltrates porous lithium ion solid electrolyte hole
It is interior；Stop insulation, be down to room temperature, after lithium metal solidification, encapsulant is set in porous ceramic support open at one end；Utilize silver
Slurry（As current collector）Cell cathode lead is Nian Jie with stephanoporate framework；Complete the making of all solid state lithium-air battery.
The all solid state lithium-air battery that will be made, static 2~4 hours in air or purity oxygen, then utilize charge and discharge
Electric instrument, tests the charge-discharge performance of battery under different condition, and battery shows preferably forthright again.The invention also discloses upper
State all solid state lithium-air battery in atmosphere, under -20~120 DEG C of use environments, the application as battery.Prepared by the present invention
Charge-discharge performance is excellent under all solid state lithium-air battery different condition, battery under different temperatures range intervals, different current densities
Output performance is excellent, stability is good.
Because above-mentioned technical proposal is used, the present invention has following advantages compared with prior art：
1st, the present invention provides one kind and is based on carbuncle type Li first7La3Zr2O12And its B positions dopant Li7La3Zr2- xMxO12The all solid state lithium-air battery of (M=Ta, Nb, Sb, Bi, Ti, Y, Al etc.) lithium ion solid electrolyte, metal
Lithium anode and solid electrolyte chemical compatibility, avoid the use of barrier film and organic electrolyte, realize whole battery real meaning
On it is all solid state, be advantageous to improve battery security performance.
2nd, all solid state lithium-air battery preparation method provided by the invention is novel, first with lithium ion solid electrolyte material
Material makes stephanoporate framework, then cathod catalyst and lithium metal are separately positioned on into stephanoporate framework outside and inner chamber, makes negative electrode
And anode, electrode is so made, lithium ion can be caused to be changed into three-dimensional transmission by two dimension transmission, expanded the three of electrode reaction
Boundary, advantageously reduce the polarization resistance of battery；Dense electrolyte layer thickness is reduced to less than 30 microns by existing grade,
Lithium ion transport path is highly shortened, advantageously reduces the Ohmic resistance of battery.
3rd, in all solid state lithium-air battery provided by the invention, whole battery structure be one end closing tubular structure, lithium
Metal anode is poured into pipe, is sealed using waterproof material；Compared to existing button cell, structure of the invention is easy to electricity
Pond encapsulates, it is possible to achieve lithium anodes and reactant gas it is completely isolated, avoid the generation of side reaction, extend battery and use
Life-span.
4th, the present invention by way of successively sintering, will form lithium-air battery each essential elements combination, adjacent layer it
Between interface it is firm, increase the structural stability of battery；Pass through the design of porous layer so that the distribution of lithium metal and catalyst is more
For solid, the transmission path of lithium ion is effectively increased；So as to which the electrical property of all-solid-state battery, stability in use greatly improved
And security.
5th, all solid state lithium-air battery selection provided by the invention is reasonable, solid dielectric material and cathod catalyst material
Material brings out the best in each other, and not only improves generation oxidate for lithium or lithium peroxide, can cause the oxidate for lithium or lithium of generation again
Peroxide decomposes again, generates oxygen and lithium metal, realizes the reversible transition put and filled, and obtained battery performance is excellent, gram
The defects of existing solid state battery is unstable, performance is bad is taken；Therefore all solid state lithium-air battery disclosed by the invention uses temperature
It is wider to spend scope, reachable -20~120 DEG C, achieves unexpected technique effect.
Brief description of the drawings
Fig. 1 is the structural representation of all solid state lithium-air battery of the present invention；
Fig. 2 is the structural representation of all solid state lithium-air battery cross section of the present invention；
Wherein, lithium anodes 1, porous ceramic support 2, thin dense electrolyte film 3, porous cathode film 4, sealing material
Material 5, galvanic anode lead 6, cell cathode lead 7, current collector 8；
Fig. 3 is the microscopic appearance figure of all solid state lithium-air battery (without filling lithium metal anode) prepared by embodiment one；
Fig. 4 is first charge-discharge curve of all solid state lithium-air battery of the preparation of embodiment one under different current densities
Figure；
Fig. 5 is the microscopic appearance figure on all solid state lithium-air battery thin dense electrolyte film surface prepared by embodiment two；
Fig. 6 be embodiment two prepare all solid state lithium-air battery at different temperatures, 200 mA cm-2Under current density
First charge-discharge curve map；
Fig. 7 is all solid state lithium-air battery of the preparation of embodiment three in 400 mA cm-2Stable charge/discharge under current density
Linearity curve figure；
Fig. 8 is AC impedance figure of all solid state lithium-air battery of the preparation of embodiment three before and after discharge and recharge；
Fig. 9 is all solid state lithium-air battery of example IV preparation in 300 mA cm-2Depth charge and discharge under current density
Electric curve map.
Embodiment
Below in conjunction with the accompanying drawings, the invention will be further described for embodiment：
1. the present invention uses S-4700 SEM (the Scan Electron of HIT
Microscope, SEM) the air electrode microstructure of preparation is observed；Using X x ray diffractions (X-Ray
Diffraction, XRD) to the catalyst progress thing phase of preparation and structural analysis, specifically test in Philips Model
Carried out on PW1830 X-ray diffractometers, condition of work is：Radiate Cu KαTarget, pipe pressure 40kV, tube current 40mA, scope 20-
80°。
2. all solid state lithium-air battery assembling provided by the invention is to be connected with high-purity argon gas（99.999%）Glove box
Interior progress, battery testing are to carry out in atmosphere.Battery charging and discharging test is in blue electric discharge and recharge instrument (the LAND CT in Wuhan
Carried out on 2001A), charging/discharging voltage scope is 2.2-4.5V, and charging and discharging currents density is 100-1000mA/g.Cyclic voltammetric is surveyed
Examination and ac impedance measurement are carried out on Shanghai Chen Hua CHI 604B electrochemical workstations.The electric current that battery charging and discharging uses with
And the specific capacity of battery is calculated with air electrode effective area.
Battery lead, current collector, the sign of encapsulant are omitted referring to accompanying drawing 1-2, wherein Fig. 2；The present invention's is complete
Solid-state lithium-air battery include lithium anodes 1, porous ceramic support 2, thin dense electrolyte film 3, porous cathode film 4,
Encapsulant 5, galvanic anode lead 6 and cell cathode lead 7, current collector 8；Porous ceramic support is closed for one end
Tubular structure；Lithium anodes are located in porous ceramic support inner chamber and hole；It is radially square in porous ceramic support
To from inside to outside, the diameter in hole tapers into, and changes in gradient；Thin dense electrolyte film is located on the outside of porous ceramic support
Wall；Porous cathode film is located at thin dense electrolyte film lateral wall；Encapsulant is located at one end of porous ceramic support opening；
The distance between porous cathode film and porous ceramic support edge of opening are 3~10mm, to avoid negative electrode and anode in electricity
Solve short circuit at matter tube opening.
Embodiment one
The g Li of precise 3.67La3Zr2O12With 0.8 g polyether sulfones (PESf), 3.6 g N, N- dimethyl pyrazoles are added
Pyrrolidone (NMP) is placed in agate jar, ball milling 4h, obtains uniform viscous paste, slurry is transferred in test tube, use diameter
About 0.3 cm glass bar dipping sizing agent, after lifting out, at the uniform velocity rotate, after thickness is uniform, be soaked into pure water rapidly
In, occur inversion of phases process, immersion 20 minutes after, take out glass bar, obtain one end closing tubular type green compact, finally with 1 DEG C/
Min heating rate, 12 h are sintered at 1050 DEG C, obtain the tubular porous ceramic supporting body of one end closing.Supporter length 4
Cm, the cm of external diameter 0.6.
The g Li of precise 1.477La3Zr2O12, 0.042 g triethanolamines, 0.054 g dibutyl phthalates,
0.054 g polyethylene glycol, 0.06 g polyvinyl butyral resins, 4.32 g ethanol are placed in agate jar, ball milling 4h, are obtained
Homogenate material；Then the slurry that the tubular porous ceramic supporting body dipping closed with one end is matched somebody with somebody, takes out drying, impregnates, dries again,
Such step operates 3 times repeatedly, finally with 1 DEG C/min heating rate, 12 h is sintered at 1150 DEG C, the pipe closed at one end
Formula porous ceramic support surface obtains the thin dense electrolyte film that thickness is about 15 microns.
The g Li of precise 0.67La3Zr2O12With 0.4 g graphite, 0.5g ethyl celluloses-terpinol binding agent is added,
Grind uniform viscous paste, using brushing method by the slurry brush on thin dense electrolyte film surface, drying, then with 1 DEG C/
Min heating rate, 6 h are sintered at 1050 DEG C, obtain the stephanoporate framework that thickness is about 60 μm.It is added dropwise in toward stephanoporate framework
The mixed aqueous solution of cobalt nitrate and ferric nitrate, drying, then is added dropwise, dries, and is repeated 3 times, then 400 DEG C of calcining 2h in atmosphere,
FeCo is grown in stephanoporate framework surface in situ2O4Nanoparticle catalyst, so as to obtain porous cathode film.Fig. 3 is above-mentioned complete solid
The microscopic appearance figure of state lithium-air battery (without filling lithium metal anode, not preparing battery lead).In being clearly seen
Layer is the porous ceramic support of pore structure gradient change, and centre is the thin dense electrolyte film that thickness is~15 μm, and outer layer is
Porous cathode film；Therefore lithium metal can be infiltrated through in porous ceramic support areole, and catalyst can be carried on porous
On skeleton hole wall, so as to form more three-dimensional distribution, the performance of battery greatly improved.
In porous cathode film surface brush thin layer silver paste, filamentary silver is stained with, 600 DEG C of calcining 0.5h, system in Muffle furnace
Make air electrode current collector and lead.In in the glove box full of high-purity argon gas（Oxygen and water vapour content are less than
1ppm）, lithium metal is carefully melted into (180.54 DEG C), and the tubular porous ceramic support intracoelomic cavity of one end closing is injected, 185
Half an hour is incubated at DEG C, ensures that molten metal lithium is fully infiltrated into hole, while filamentary silver is inserted in molten state lithium metal, with
After be down to room temperature, make lithium anodes.With bicomponent epoxy resin AB glue adhesive to lithium anodes in glove box
Sealed, complete the making of all solid state lithium-air battery.
The all solid state lithium-air battery made is taken out out of glove box, in atmosphere static 2h, then utilize discharge and recharge
Instrument, test the charge-discharge performance of battery under different condition.
Fig. 4 is first charge-discharge curve of the above-mentioned all solid state lithium-air battery under different current densities, and battery is shown
It is preferably forthright again.
Embodiment two
The g Li of precise 7.26.5La3Zr1.5Ta0.5O12With 1.6 g polyether sulfones (PESf), 7.2 g N, N- bis- are added
Methyl pyrrolidone (NMP) is placed in agate jar, ball milling 4h, obtains uniform viscous paste, slurry is transferred in test tube,
The glass bar dipping sizing agent for being about 0.8 cm with diameter, after lifting out, at the uniform velocity rotate, after thickness is uniform, be soaked into rapidly
In pure water, occur inversion of phases process, immersion 20 minutes after, take out glass bar, obtain one end closing tubular type green compact, finally with
1 DEG C/min heating rate, 16 h are sintered at 1050 DEG C, obtain the tubular porous ceramic supporting body of one end closing.Supporter
Long 6 cm, the cm of external diameter 1.2.
The g Li of precise 1.476.5La3Zr1.5Ta0.5O12, 0.042 g triethanolamines, 0.054 g phthalic acids two
Butyl ester, 0.054 g polyethylene glycol, 0.06 g polyvinyl butyral resins, 4.32 g ethanol are placed in agate jar, ball milling 4h,
Obtain uniform sizing material；Then the slurry that the tubular porous ceramic supporting body dipping closed with one end is matched somebody with somebody, takes out drying, soaks again
Stain, drying, such step operate 4 times repeatedly, finally with 1 DEG C/min heating rate, 12 h are sintered at 1200 DEG C, at one end
The tubular porous ceramic support external surface of closing obtains the thin dense electrolyte film that thickness is about 20 μm.Fig. 5 is above-mentioned complete solid
The microscopic appearance on state lithium-air battery thin dense electrolyte film surface, it can be seen that electrolyte is fine and close.
The g Li of precise 0.66.5La3Zr1.5Ta0.5O12With 0.4 g graphite, 0.5g ethyl celluloses-terpinol is added
Binding agent, uniform viscous paste is ground, using brushing method by the slurry brush on thin dense electrolyte film surface, drying, then
With 1 DEG C/min heating rate, 6 h are sintered at 1050 DEG C, obtain the stephanoporate framework that air electrode thickness is about 60 μm.It is past
The mixed aqueous solution of manganese acetate and cobalt nitrate, drying are added dropwise in stephanoporate framework, then is added dropwise, dries, is repeated 4 times, then in air
In 450 DEG C calcining 4h, stephanoporate framework surface in situ grow MnCo2O4Nanoparticle catalyst is thin so as to obtain porous cathode
Film.
In porous cathode film surface brush thin layer silver paste, filamentary silver is stained with, 600 DEG C of calcining 0.5h, system in Muffle furnace
Make air electrode current collector and lead.The half-cell for having made air electrode is transferred to the gloves full of high-purity argon gas
In case（Oxygen and water vapour content are less than 1ppm）, lithium metal is carefully melted into (180.54 DEG C), and be transferred to tubular porous pottery
In porcelain supporter pipe, half an hour is incubated at 185 DEG C, ensures that molten metal lithium fully infiltrates porous pipe type porous ceramics branch
In support body hole, while filamentary silver is inserted in molten state lithium metal, be subsequently reduced to room temperature, make lithium anodes.In glove box
It is interior that lithium anodes are sealed with bicomponent epoxy resin AB glue adhesive, complete the making of all solid state lithium-air battery.
The all solid state lithium-air battery made is taken out out of glove box, in atmosphere static 3h, then utilize discharge and recharge
Instrument, test the charge-discharge performance of battery under different condition.
Fig. 6 be all solid state lithium-air battery at different temperatures, 200 mA cm-2Filling first under current density
Discharge curve.As can be seen that the raising of operating temperature, battery charging and discharging capacity improves.
Embodiment three
The g Li of precise 7.26La3Ta1.5Y0.5O12With 1.6 g polyether sulfones (PESf), 7.2 g N, N- diformazans are added
Base pyrrolidones (NMP) is placed in agate jar, ball milling 4h, obtains uniform viscous paste, slurry is transferred in test tube, is used
The glass bar dipping sizing agent that diameter is about 0.6 cm, after lifting out, at the uniform velocity rotate, after thickness is uniform, be soaked into rapidly pure
In water purification, inversion of phases process occurs, after soaking 20 minutes, takes out glass bar, the tubular type green compact of one end closing is obtained, finally with 1
DEG C/min heating rate, 24 h are sintered at 1050 DEG C, obtain the tubular porous ceramic supporting body of one end closing.Supporter is grown
8 cm, the cm of external diameter 1.0.
The g Li of precise 1.476La3Ta1.5Y0.5O12, 0.042 g triethanolamines, the fourth of 0.054 g phthalic acids two
Ester, 0.054 g polyethylene glycol, 0.06 g polyvinyl butyral resins, 4.32 g ethanol are placed in agate jar, ball milling 4h, obtained
To uniform sizing material；Then the slurry matched somebody with somebody with LLTYO tubular porous supporter dipping, takes out drying, impregnates, dries again, so
Step operates 6 times repeatedly, finally with 1 DEG C/min heating rate, 12 h is sintered at 1200 DEG C, the tubular type closed at one end is more
Hole ceramic supporting body lateral wall obtains the thin dense electrolyte film that thickness is about 30 um.
The g Li of precise 0.76La3Ta1.5Y0.5O12With 0.3 g graphite, add 0.5g ethyl celluloses-terpinol and glue
Agent is tied, grinds uniform viscous paste, using brushing method by the slurry brush in thin dense electrolyte film surface, drying, then with 1
DEG C/min heating rate, 6 h are sintered at 1050 DEG C, obtain the stephanoporate framework that air electrode thickness is about 60 um.It is past porous
The mixed aqueous solution of cobalt nitrate and nickel nitrate, drying are added dropwise in skeleton, then is added dropwise, dries, is repeated 4 times, then in atmosphere 400
DEG C calcining 2h, stephanoporate framework surface in situ grow NiCo2O4Nanoparticle catalyst, so as to obtain porous cathode film.
In porous cathode film surface brush thin layer silver paste, filamentary silver is stained with, 600 DEG C of calcining 0.5h, system in Muffle furnace
Make air electrode current collector and lead.The half-cell for having made air electrode is transferred to the gloves full of high-purity argon gas
In case（Oxygen and water vapour content are less than 1ppm）, carefully lithium metal is melted, and be transferred to the tubular porous pottery of one end closing
In porcelain supporter pipe, half an hour is incubated at 185 DEG C, ensures that molten metal lithium fully infiltrates porous ceramic support hole
It is interior, while filamentary silver is inserted in molten state lithium metal, room temperature is subsequently reduced to, makes lithium anodes.Liquid is used in glove box
Body paraffin seals to lithium anodes, completes the making of all solid state lithium-air battery.
The all solid state lithium-air battery made is taken out out of glove box, in atmosphere static 2h, then utilize discharge and recharge
Instrument, test the charge-discharge performance of battery under different condition.
Fig. 7 is above-mentioned all solid state lithium-air battery in 400 mA cm-2Stable charge/discharge linearity curve under current density.Can be with
Find out, after 15 circle circulations, battery capacity does not decay.Fig. 8 is friendship of the above-mentioned all solid state lithium-air battery before and after discharge and recharge
Flow impedance figure.As can be seen that electric discharge after, cell resistance increased, but charge after, resistance reduces again, show battery with compared with
Good recyclability.
Example IV
The g Li of precise 7.26La3Zr1.75Nb0.25O12With 1.6 g polyether sulfones (PESf), 7.2 g N, N- bis- are added
Methyl pyrrolidone (NMP) is placed in agate jar, ball milling 4h, obtains uniform viscous paste, slurry is transferred in test tube,
The glass bar dipping sizing agent for being about 0.8 cm with diameter, after lifting out, at the uniform velocity rotate, after thickness is uniform, be soaked into rapidly
In pure water, occur inversion of phases process, immersion 25 minutes after, take out glass bar, obtain one end closing tubular type green compact, finally with
1 DEG C/min heating rate, 12 h are sintered at 1100 DEG C, obtain the tubular porous ceramic supporting body of one end closing.Supporter
Long 8 cm, the cm of external diameter 1.5.
The g Li of precise 1.476La3Zr1.75Nb0.25O12, 0.042 g triethanolamines, 0.054 g phthalic acids two
Butyl ester, 0.054 g polyethylene glycol, 0.06 g polyvinyl butyral resins, 4.32 g ethanol are placed in agate jar, ball milling 4h,
Obtain uniform sizing material；Then the slurry that the tubular porous ceramic supporting body dipping closed with one end is matched somebody with somebody, takes out drying, soaks again
Stain, drying, such step operate 5 times repeatedly, finally with 1 DEG C/min heating rate, 8 h are sintered at 1200 DEG C, at one end
The tubular porous ceramic support external surface of closing obtains the thin dense electrolyte film that thickness is about 25 um.
The g Li of precise 0.56La3Zr1.75Nb0.25O12With 0.5 g graphite, 0.5g ethyl celluloses-terpinol is added
Binding agent, uniform viscous paste is ground, using brushing method by the slurry brush on thin dense electrolyte film surface, drying, then
With 1 DEG C/min heating rate, 6 h are sintered at 1050 DEG C, obtain the stephanoporate framework that air electrode thickness is about 60 um.Will
The mixed aqueous solution of barium nitrate, strontium nitrate, cobalt nitrate and ferric nitrate, drying are impregnated in hole on framework, then impregnates, dry, repeats 6
It is secondary, then in atmosphere 600 DEG C calcining 4h, stephanoporate framework surface in situ grow Ba0.5Sr0.5Co0.8Fe0.2O3Nano particle is urged
Agent, so as to obtain porous cathode film.
In porous cathode film surface brush thin layer silver paste, filamentary silver is stained with, 600 DEG C of calcining 0.5h, system in Muffle furnace
Make air electrode current collector and lead.The half-cell for having made air electrode is transferred to the gloves full of high-purity argon gas
In case（Oxygen and water vapour content are less than 1ppm）, carefully lithium metal is melted, and be transferred to the tubular porous pottery of one end closing
In porcelain supporter pipe, half an hour is incubated at 185 DEG C, ensures that molten metal lithium fully infiltrates porous ceramic support hole
It is interior, while filamentary silver is inserted in molten state lithium metal, room temperature is subsequently reduced to, makes lithium anodes.Liquid is used in glove box
Body paraffin seals to lithium anodes, completes the making of all solid state lithium-air battery.
The all solid state lithium-air battery made is taken out out of glove box, in atmosphere static 2h, then utilize discharge and recharge
Instrument, test the charge-discharge performance of battery under different condition.
Fig. 9 is above-mentioned all solid state lithium-air battery in 300 mA cm-2Depth charging and discharging curve figure under current density.Can
To find out, after 5 depth charge-discharge tests, capacity is maintained at more than 50%, shows that battery has preferable cyclicity.
Claims (10)
- A kind of 1. all solid state lithium-air battery, it is characterised in that：The all solid state lithium-air battery includes lithium anodes, more Hole ceramic supporting body, thin dense electrolyte film, porous cathode film, encapsulant, current collector, galvanic anode lead and Cell cathode lead；The porous cathode film includes stephanoporate framework and the cathod catalyst being carried on stephanoporate framework；Institute State the tubular structure that porous ceramic support is one end closing；The lithium anodes be located at the inner chamber of porous ceramic support with And in hole；The thin dense electrolyte film is located at porous ceramic support lateral wall；The porous cathode film is positioned at fine and close electricity Solve matter film outside wall；The encapsulant is located at one end of porous ceramic support opening；The porous ceramic support Material is carbuncle type lithium ion solid electrolyte material；The material of the thin dense electrolyte film is that carbuncle type lithium ion is consolidated State electrolyte.
- 2. all solid state lithium-air battery according to claim 1, it is characterised in that：In the porous ceramic support, along footpath To direction, from inside to outside, aperture tapers into；Between the porous cathode film and porous ceramic support edge of opening away from From for 3~10mm.
- 3. all solid state lithium-air battery according to claim 1, it is characterised in that：The wall thickness of the porous ceramic support For 1~3mm, draw ratio is（0.06~0.5）∶1；The thickness of the thin dense electrolyte film is 2~30 μm；The stephanoporate framework Porosity be 50~80%；The thickness of the porous cathode film is 30~150 μm.
- 4. the preparation method of all solid state lithium-air battery described in claim 1, it is characterised in that comprise the following steps：（1）In the presence of consisting of phase-transferring agent, using carbuncle type lithium ion solid electrolyte material as raw material, porous ceramic support is prepared Body green compact；Then green compact are sintered 12~24 hours in 1000~1100 DEG C, obtains porous ceramic support；（2）In the presence of organic additive, carbuncle type lithium ion solid electrolyte material is scattered in organic solvent, obtained Dipping sizing agent；Then by step（1）Porous ceramic support be impregnated in the dipping sizing agent；After the completion of dipping, in 1000 ~1250 DEG C sinter 8~12 hours, i.e., form thin dense electrolyte film in porous ceramic support lateral wall；（3）The raw material for preparing cathod catalyst is added to the water, is configured to cathod catalyst precursor solution；By carbuncle type lithium Ion solid electrolyte material, bonding agent and pore creating material mixing, prepare and apply slurry；Then slurry will be applied and be painted on step （2）Obtained thin dense electrolyte film surface；After the completion of brushing, sintered in 1000~1100 DEG C 4~8 hours, i.e., in fine and close electricity Solve matter film surface and form stephanoporate framework；By stephanoporate framework and cathod catalyst precursor solution it is compound after, by calcining so that Cathod catalyst is carried on stephanoporate framework；（4）By lithium metal liquation implantation step（3）Porous ceramic support inner chamber in, then by galvanic anode lead insert gold Belong in lithium liquation；After lithium metal solidification, encapsulant is set in porous ceramic support open at one end；Then silver paste is utilized by electricity Pool cathode lead is Nian Jie with stephanoporate framework；Obtain all solid lithium-air cell.
- 5. the preparation method of all solid state lithium-air battery according to claim 4, it is characterised in that：Step（1）In, by phase Transfer agent is ground uniformly after being mixed with carbuncle type lithium ion solid electrolyte material, then prepares porous ceramic support life Base；The consisting of phase-transferring agent is polyether sulfone powder；The mass ratio of consisting of phase-transferring agent and carbuncle type lithium ion solid electrolyte material is 0.8~1.2: 1.
- 6. the preparation method of all solid state lithium-air battery according to claim 4, it is characterised in that：Step（2）In, having In the presence of machine additive, carbuncle type lithium ion solid electrolyte material is scattered in organic solvent, ball milling 3~5 hours, obtained To dipping sizing agent；The number that porous ceramic support is impregnated in the dipping sizing agent is 2~6 times, is dried again after dipping every time Impregnated next time；The organic additive is triethanolamine, dibutyl phthalate, polyethylene glycol, polyvinyl alcohol contracting One or more in butyraldehyde；The organic solvent is alcoholic solvent；The dosage of the organic additive is carbuncle type lithium ion The 14%~15% of solid electrolyte material quality.
- 7. the preparation method of all solid state lithium-air battery according to claim 4, it is characterised in that：Step（3）In, it is described Pore creating material is activated carbon or starch；The dosage of the pore creating material is the 40 of carbuncle type lithium ion solid electrolyte material quality ~100%；Stephanoporate framework is by stephanoporate framework impregnated cathode complex catalyst precursor with the compound mode of cathod catalyst precursor solution Dripped in liquid solution or by cathod catalyst precursor solution on stephanoporate framework；Calcining heat is 380~650 DEG C, the time 2 ~8 hours.
- 8. the preparation method of all solid state lithium-air battery according to claim 4, it is characterised in that：Step（4）In, filling Have in the glove box of argon gas, oxygen and water vapour content less than 1ppm, by lithium metal liquation implantation step（3）Porous ceramics branch In support body inner chamber, then galvanic anode lead is inserted in lithium metal；20~40 minutes are incubated in 185 DEG C；Stop insulation, metal After lithium solidification, encapsulant is set in porous ceramic support open at one end.
- 9. the preparation method of all solid state lithium-air battery according to claim 4, it is characterised in that：The carbuncle type lithium Ion solid electrolyte material is Li7La3Zr2O12Or Li7La3Zr2-xMxO12, wherein M be Ta, Nb, Sb, Bi, Ti, Y or Al；The galvanic anode lead is silver wire；The cell cathode lead is silver wire；The cathod catalyst is spinel oxide Or perovskite oxide；The encapsulant is paraffin or bicomponent epoxy resin adhesive.
- 10. application of all solid state lithium-air battery as battery described in claim 1, it is characterised in that：The application environment is Air, temperature limit are -20~120 DEG C.
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| CN106960993B (en) * | 2017-03-09 | 2019-05-24 | 上海空间电源研究所 | Lithium-air battery and its test device |
| CN106848391B (en) * | 2017-03-15 | 2019-05-14 | 郑州新世纪材料基因组工程研究院有限公司 | A kind of lithium ion battery solid electrolyte and preparation method thereof |
| WO2019074538A1 (en) * | 2017-10-09 | 2019-04-18 | Lawrence Livermore National Security, Llc | Three-dimensional rechargeable battery with solid-state electrolyte |
| CN107819149A (en) * | 2017-11-09 | 2018-03-20 | 天津工业大学 | A kind of method that growth in situ prepares all-solid sodium ion battery |
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| US11942622B2 (en) * | 2020-09-18 | 2024-03-26 | The Regents Of The University Of California | Methods of fabricating porous ceramic electrodes for solid state battery applications |
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