CN105140541B - Soap-free emulsion polymeization formulation air electrode for lithium air battery and preparation method and application - Google Patents
Soap-free emulsion polymeization formulation air electrode for lithium air battery and preparation method and application Download PDFInfo
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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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
- H01M8/0236—Glass; Ceramics; Cermets
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- H—ELECTRICITY
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- 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a kind of soap-free emulsion polymeization formulation air electrode for lithium air battery and preparation method and application, air electrode catalyst is grown on porous metalloceramic skeleton.The air electrode for lithium air battery preparation method that the present invention is provided eliminates the accessory substance brought in battery charge and discharge process by binding agent without using high polymer binder；Not carbonaceous material in electrode, it is to avoid the caused cell performance decay of carbon material corrosion in battery charging process；Air electrode catalyst is grown directly upon on cermet skeleton, difficult for drop-off in charge and discharge process or reunion, and contacts close between catalyst and current collector, and cell contact resistance is small.The lithium-air battery that the air electrode prepared using the inventive method is assembled has charge/discharge capacity high, good rate capability, the advantages of cyclical stability is high, it is adaptable to various mobile electronic device and electrokinetic cell fields.
Description
Technical field
The present invention relates to a kind of lithium-air battery air electrode, and in particular to a kind of soap-free emulsion polymeization formulation lithium-air battery is empty
Pneumoelectric pole and preparation method and application, belongs to high performance chemical electric power source field.
Background technology
Because the fast-developing and modern people in the fields such as space technology, mobile communication, guided missile, Aero-Space are to the energy
Crisis, the care of environmental protection, research, the exploitation of high energy-storage battery have caused the extensive concern of people.Because lithium is all
Quality minimum, electrode potential are minimum in metallic element, so the battery being made up of lithium has open-circuit voltage height, specific discharge capacity big
The features such as, NI-G, Ni-MH battery are instead of recent years rapidly as most popular high-energy battery.
Lithium-air battery be it is a kind of using oxygen as positive electrode active materials, using lithium metal as the battery of negative active core-shell material,
Because oxygen need not be stored in inside battery, 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.Aerial oxygen can be become negative oxygen ion by catalyst or cross negative oxygen ion, so
Regeneration oxidate for lithium or lithium peroxide, different with conventional aluminium-air cell, zinc-air battery afterwards；Therefore lithium-air
Before battery has wide application as high-energy-density power supply of new generation in the field such as portable type electronic product and communication apparatus
Scape, can especially meet the requirement of the high-energy-density of electric car power supply.
In lithium-air battery discharge process, the polarization of lithium metal anode is generally relatively low, and peroxide and lithia are insoluble
Solution is only precipitated in organic electrolyte on air electrode, as the oxygen electrode of negative electrode to the chemical property of battery (such as：Fill
Discharge performance, coulombic efficiency, cyclical stability etc.) often there is decisive influence.
Oxygen electrode occurs that the place of oxygen evolution reaction occurs when oxygen reduction reaction and charging when being lithium-air battery electric discharge,
In the presence of typical gas-liquid-solid phase reaction interface area, not only the diffusion impedance of oxygen and activation polarization are larger in course of reaction, and
Metal oxide can be deposited and be enriched with oxygen electrode surface, hinder even to prevent contact of the oxonium ion with metal ion and make electrode
Reaction terminating.At present, the subject matter that the lithium-air battery of organic electrolyte system exists in use is：Discharged
The Li generated in journey2O2Or Li2O oxides can deposit and be attached to catalyst surface and prevent oxygen from directly connecting again with catalyst
Touch, cause slowing down or even termination for oxygen reduction reaction；Li2O2Or Li2O oxide conductings are poor, and electrode polarization is big；Electric discharge
When oxygen reduction reaction and charging when oxygen evolution reaction dynamic performance it is poor, battery efficiency is low；Cycle performance difference etc..For
Solve these practical problems, improve oxygen electro-catalysis efficiency and battery can reverse efficiency, current research work is concentrated mainly on
In terms of the exploitation of air electrode catalyst and the optimization of air electrode preparation technology.It is substantial amounts of in terms of efficient elctro-catalyst
Research have shown the noble metals such as platinum ruthenium and alloy (referring to：J. AM. Chem. Soc, 2010, 132:12170), exotic atom
Doping carbon material (referring to：Nano Letters, 2011, 11:5071; ACS Applied Materials &
Interfaces, 2012, 4:49), spinel oxide (CN103346333A) and perovskite oxide
(CN103268947A;) etc. CN103208636A there is preferable catalytic activity to hydrogen reduction/evolution reaction.
Performance of the preparation of air electrode to its performance has a major impact, and is not only related to the pore-size distribution of supporter, more
It is related to catalyst and supports situation on supporter, occurring oxygen when oxygen reduction reaction and charging when these can all be related to electric discharge separates out
The efficiency of reaction, so as to influence the performance of battery.In terms of air electrode making, the existing electrode fabrication technology of lithium-air battery
It is main using technologies such as spraying, blade coatings, by using high polymer binder by air electrode catalyst it is scattered stick to carbon paper or
The conductive carbon material such as carbon cloth surface.Existing air electrode preparation method has following several respects defect：1. make as binding agent
High polymer material easily causes the generation of other side reactions in lithium-air battery charge and discharge process；2. air electrode is urged
It is combined together between agent and conductive carbon material simply by the effect of binding agent, gas is accompanied by battery charging process
Effusion, discharge and recharge repeatedly, it is easy to cause coming off for catalyst, and contact not close between catalyst and carbon material, contact
Resistance is big, influence battery charging and discharging performance and cycle performance；3. the carbon used as electrode support skeleton and current collector
Paper or carbon cloth, under the higher charging voltage of battery, carbon material is easily oxidized corrosion, and triggers the decomposition of organic electrolyte, makes
Into cell performance decay；4. existing cladding process prepares air electrode, catalyst solids easily gather, skewness, and
And thickener can not be well immersed in supporter hole, catalyst only floats over supporting body surface, causes battery charging and discharging unstable.Cause
This, on the basis of existing air electrode catalyst, optimization air electrode preparation technology is to improve the weight of lithium-air battery performance
Want one of approach.
The content of the invention
It is an object of the invention to provide a kind of preparation method of soap-free emulsion polymeization formulation lithium-air battery air electrode, to reduce
The generation of side reaction in battery charge and discharge process, improves battery charging and discharging capacity and stability.
To achieve the above object of the invention, the technical solution adopted by the present invention is：
A kind of preparation method of soap-free emulsion polymeization formulation lithium-air battery air electrode, comprises the following steps：
（1）Using nickel oxide and oxygen ion conductor material as raw material, the porous nickel oxide that thickness is 200~800 microns is prepared
The mass ratio of ceramics, wherein nickel oxide and oxygen ion conductor material is（1~4）∶1；
（2）The raw material for preparing lithium-air battery air electrode catalyst is added to the water, solution is configured to；Lithium-the sky
Pneumoelectric pond air electrode catalyst is perovskite oxide；Total metal particle concentrations are 0.2~2mol/L in the solution；
（3）By solution described in the porous nickel oxide cerdip, take out and calcined after drying, last sintered processing is obtained
Support the porous nickel oxide ceramics of lithium-air battery air electrode catalyst；
（4）The porous nickel oxide ceramics for supporting lithium-air battery air electrode catalyst are mixed by hydrogen or argon hydrogen
Soap-free emulsion polymeization formulation lithium-air battery air electrode is obtained after closing gas annealing processing.
In above-mentioned technical proposal, step（1）In, after nickel oxide and oxygen ion conductor material are mixed, using Mechanical pressing
Method or the tape casting prepare green compact, and porous nickel oxide ceramics are obtained after green compact are sintered.
In above-mentioned technical proposal, when preparing green compact using Mechanical pressing method, using graphite or starch as pore creating material；Using stream
When the method for prolonging prepares green compact, using dimethylbenzene as solvent, polyvinyl butyral resin is binding agent, dibutyl phthalate and poly- second two
Alcohol is plasticizer, and oleic acid is dispersant, and tributyl phosphate is defrother.
In above-mentioned technical proposal, step（1）In, the oxygen ion conductor material is CeO2、Sm0.2Ce0.8O1.9、
Gd0.2Ce0.8O1.9、La0.8Sr0.2Ga0.85Mg0.15O3Or 8mol%Y2O3-ZrO2(YSZ)。8mol%Y2O3-ZrO2Refer to 8mol%
Y2O3Stable ZrO2。
In above-mentioned technical proposal, step（2）In, the lithium-air battery air electrode catalyst is
Ba0.9Co0.7Fe0.2Nb0.1O3、La0.8Sr0.2MnO3、La0.6Sr0.4Co0.2Fe0.8O3、Ba0.5Sr0.5Co0.8Fe0.2O3、
La0.75Sr0.25Cr0.5Mn0.5O3、 Ln0.4Sr0.6Co0.2Fe0.7Nb0.1O3Or Sr2M2-xMoxO6；Wherein Ln be La, Pr or
Sm；M is Fe, Co, Cr, Mg or Mn；X is 0~2 and not including 0,2.It is preferred that, the lithium-air battery air electrode is urged
Agent is La0.75Sr0.25Cr0.5Mn0.5O3Or Ln0.4Sr0.6Co0.2Fe0.7Nb0.1O3Or Sr2M2-xMoxO6.Prepare the lithium-
The raw material of air cell air electrode catalyst is not particularly limited, and those skilled in the art can select according to element ratio.
In order to improve catalyst effect, step are supported on porous nickel oxide ceramics（3）In, by the porous nickel oxide
Cerdip a period of time in the solution, take out and calcined after drying；Then the porous nickel oxide ceramics after calcining are continued
The solution is impregnated in, is calcined again after taking out drying；Such step is repeated 3~6 times；Finally sintered processing is supported again
The porous oxidation nickel cermet of lithium-air battery air electrode catalyst.Dip time is not specially required, can be according to molten
Liquid concentration and number of repetition selection.
In above-mentioned technical proposal, step（3）In, the calcining is calcined 2 hours for 600~650 DEG C；It is described to be sintered to 900
~1000 DEG C sinter 4~8 hours；Step（4）In, the annealing is handled 4 hours for 800~950 DEG C.
The invention also discloses the soap-free emulsion polymeization type lithium-air battery air electrode prepared according to above-mentioned preparation method, by many
Hole nickel cermet and the lithium-air battery air electrode catalyst supported on the porous nickel metal is ceramic are constituted；Institute
State in soap-free emulsion polymeization formulation lithium-air battery air electrode, the mass fraction of catalyst is 0.2~2%；The porous nickel metal pottery
The porosity of porcelain is 40~80%.Porous nickel metal ceramics are as supporter and current collector, and porosity is high, supports urge thereon
Agent collectively forms lithium-air battery air electrode, without bonding agent, lithium-air battery stable charge/discharge prepared therefrom, electricity
Pond specific capacity is high, therefore the application the invention also discloses above-mentioned soap-free emulsion polymeization formulation air electrode in lithium-air battery is prepared.
In above-mentioned technical proposal, annealing can provide electrode conductivuty, while increasing perovskite catalyst Lacking oxygen
Concentration, improves catalytic activity.The present invention directly prepares lithium-air battery air electrode on supporter from raw material first and urged
Agent, obtained catalyst is consistent with design, it is ensured that catalyst performance stabilised, is catalyzed while avoiding on existing air electrode
Agent easily gathers, be bonded the defect such as loosely, is conducive to lithium-air battery discharge and recharge safety and stability, long life.
Because above-mentioned technical proposal is used, the present invention has following advantages compared with prior art：
1st, the present invention provides a kind of soap-free emulsion polymeization formulation lithium-air battery air electrode first, it is to avoid in discharge and recharge
Side reaction in journey caused by binding agent is present occurs, and reduces air electrode relative mass, increase battery is with respect to specific energy；
Overcome adverse effect of the prior art bonding agent to lithium-air battery air electrode.
2nd, the lithium-air battery air electrode preparation method that the present invention is provided, has used non-carbon material as electrode supporting
Body and current collector, it is to avoid battery is under the higher charging voltage, and carbon material is easily oxidized corrosion, and triggers organic electrolysis
The decomposition of liquid, causes the defect of cell performance decay.
3rd, the lithium-air battery air electrode preparation method that the present invention is provided, air electrode catalyst is using solution leaching
Stain method homoepitaxial is on porous supporting body, and catalyst content is high, it is ensured that the actual composition of catalyst is consistent with Theoretical Design, carries
The high stability of catalyst；It is possible to prevente effectively from coming off or reuniting for catalyst, improves battery charge and discharge in charge and discharge process
Electrical stability；Also, contact close between air electrode catalyst and current collector, reduce cell contact resistance, improve
Battery specific capacity, discharge capacity reaches 3035mAh/g to battery first；Achieve unexpected technique effect.
4th, in lithium-air battery air electrode disclosed by the invention, catalyst feed solution being capable of complete wetting porous nickel
Supporter, is dispersed in porous nickel ceramics inside and surface by catalyst raw material by repeatedly infiltrating, passes through high-temperature process
Lithium-air battery air electrode catalyst is directly generated on porous nickel supporter, it is ensured that catalyst content in porous nickel
It is high and be evenly distributed, it is to avoid catalyst distribution that existing coating processes are caused is uneven, easily gather, it is impossible to enters and supports body opening
The defect of gap.
5th, lithium-air battery air electrode preparation method disclosed by the invention is without special installation, and conventional high temperature sintering is
Product is can obtain, catalyst supports stabilization on porous nickel metal ceramics, the use of organic matter reduced, beneficial to environmental protection, by it
The battery performance of preparation is good, is conducive to the development and application of lithium-air battery.
Brief description of the drawings
Fig. 1 is Ni-CeO prepared by embodiment 12-Sr2Fe4/3Mo2/3O6The microscopic appearance figure of air electrode；
Fig. 2 be embodiment 1 in after high-temperature calcination NiO, SFMO and NiO-SFMO XRD；
Fig. 3 is the first charge-discharge curve map of 2032 lithium-air batteries prepared by embodiment 1；
Fig. 4 is the cyclic voltammetry curve and AC impedance spectroscopy of 2032 lithium-air batteries prepared by embodiment 2；
Fig. 5 is the first charge-discharge curve map of 2032 lithium-air batteries prepared by embodiment 2；
Fig. 6 is the first charge-discharge curve map of 2032 lithium-air batteries prepared by embodiment 3；
Fig. 7 is the depth charging and discharging curve figure of 2354 lithium-air batteries prepared by embodiment 4；
Fig. 8 is the stable charge/discharge figure of 2354 lithium-air batteries prepared by embodiment 4；
Fig. 9 is the first charge-discharge curve map of 2025 lithium-air batteries prepared by embodiment 5；
Figure 10 is the XRD and microscopic appearance of Ni-GDC-LSCM air electrodes prepared by embodiment 7；
Figure 11 is the charging and discharging curve figure of lithium-air battery prepared by comparative example 1.
Embodiment
Below in conjunction with the accompanying drawings, the invention will be further described for embodiment and comparative example：
1. the present invention is using 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. the air electrode that the present invention makes is using button lithium-air battery as example when assembling lithium-air battery.
Battery assembling is to be connected with high-purity argon gas（99.999%）Glove box in carry out, battery testing is to be connected with high pure nitrogen
（99.999%, 80 Vol.%）And high purity oxygen gas（99.999%, 20 Vol.%）Glove box in carry out.Battery diaphragm is
Waterman all-glass papers, electrolyte is 1mol/L LiTFSI-TEGDME, and negative pole is metal lithium sheet.Battery charging and discharging is surveyed
Examination is carried out on the blue electric discharge and recharge instrument (LAND CT 2001A) in Wuhan, and charging/discharging voltage scope is 2.2-4.4V, discharge and recharge electricity
Current density is 100-500mA/g.Cyclic voltammetry and ac impedance measurement are in Shanghai Chen Hua CHI 604B electrochemical operations
Carried out on standing.Battery specific capacity is calculated with the catalyst quality impregnated in air electrode.
Embodiment 1：Ni-CeO2-Sr2Fe4/3Mo2/3O6Air electrode
Precise 0.7gNiO and 0.3gCeO2It is placed in mortar, adds 0.2g graphite and do pore creating material, is fully ground
It is even, 3 a diameter of 12mm green compact, each green compact quality about 0.4g, then with 2 DEG C/min's are then pressed into using tablet press machine
Heating rate, sinters 4h at 1200 DEG C, obtains NiO-CeO2Porous supporting body, thickness is 400um or so, porosity 50%.
According to Sr2Fe4/3Mo2/3O6(SFMO) stoichiometric proportion prepares the mixing that total concentration of metal ions is 1.0mol/L
The aqueous solution, raw material is Sr (NO3)2、Fe(NO3)3·9H2O and (NH4)6Mo7O24·4H2O.Then by NiO-CeO2Porous supporting body
Above-mentioned mixed solution is impregnated, takes out and calcines 2h at drying, 600 DEG C, take out, then impregnates mixed aqueous solution, dries, is forged at 600 DEG C
Burn 2h.Such step is operated 5 times repeatedly, is finally positioned over 1000 DEG C of sintering 4h in Muffle furnace.Obtaining growth on skeleton has
Sr2Fe4/3Mo2/3O6NiO-CeO2Porous supporting body（NiO-CeO2- SFMO porous supporting bodies）.
By the NiO-CeO of preparation2- SFMO porous supporting bodies are positioned in the tube furnace for be connected with high-purity hydrogen and forged at 900 DEG C
4h is burnt, Ni-CeO is finally given2- SFMO air electrodes.Sr in air electrode2Fe4/3Mo2/3O6Mass fraction is 1.2%.
Utilize the Ni-CeO of making2- SFMO air electrodes assemble 2032 lithium-air batteries and test battery charging and discharging
Energy.
Fig. 1 is Ni-CeO2The microscopic appearance figure of-SFMO air electrodes.This it appears that the Sr of generation2Fe4/3Mo2/3O6
For nano particle, Ni-CeO is evenly distributed on2Porous supporting body surface.
Fig. 2 is the XRD after NiO, SFMO and NiO-SFMO calcining.As can be seen that SFMO shapes after calcining 4h through 1000 DEG C
Into perovskite structure, and NiO and SFMO are that high temperature is compatible, do not have side reaction.
Fig. 3 is to utilize Ni-CeO22032 lithium-air batteries of-SFMO air electrodes assembling are under 200mA/g current densities
First charge-discharge curve, discharge capacity reaches 2130mAh/g to battery first.
Embodiment 2：Ni-Sm0.2Ce0.8O1.9-Sr2Co1.5Mo0.5O6Air electrode
Precise 0.5gNiO and 0.5g Sm0.2Ce0.8O1.9It is placed in mortar, adds 0.2g starch and do pore creating material, fill
Divide grinding uniform, 3 a diameter of 12mm green compact, each green compact quality about 0.4g, then with 2 are then pressed into using tablet press machine
DEG C/min heating rate, 4h is sintered at 1200 DEG C, NiO- Sm are obtained0.2Ce0.8O1.9Porous supporting body, thickness is about
500um, porosity 60%.
According to Sr2Co1.5Mo0.5O6Stoichiometric proportion prepare the mixed solution that total concentration of metal ions is 2.0mol/L, it is former
Expect for Sr (NO3)2、Co(NO3)3·6H2O and (NH4)6Mo7O24·4H2O.Then by NiO-Sm0.2Ce0.8O1.9Porous supporting body soaks
Stain enters in above-mentioned mixed solution, drying, calcines 2h at 600 DEG C, takes out, then impregnates, and dries, calcining.So operate 3 times repeatedly,
Finally it is positioned over 950 DEG C of sintering 6h in Muffle furnace.Obtaining growth on skeleton has Sr2Co1.5Mo0.5O6NiO-Sm0.2Ce0.8O1.9It is many
Hole supporter.
By the NiO-Sm of preparation0.2Ce0.8O1.9-Sr2Co1.5Mo0.5O6Porous supporting body is positioned over the pipe for being connected with high-purity hydrogen
4h is calcined at 900 DEG C in formula stove, Ni-Sm is finally given0.2Ce0.8O1.9-Sr2Co1.5Mo0.5O6Air electrode.In air electrode
Sr2Co1.5Mo0.5O6Mass fraction is 0.5%.
Utilize the Ni-Sm of making0.2Ce0.8O1.9-Sr2Co1.5Mo0.5O6Air electrode assembles 2032 lithium-air batteries and surveyed
Try battery charging and discharging performance.
Fig. 4 is Ni-Sm0.2Ce0.8O1.9-Sr2Co1.5Mo0.5O6The circulation volt of the lithium-air battery of assembling 2032 of air electrode
Pacify curve and ac impedance spectroscopy.
Fig. 5 is to utilize Ni-Sm0.2Ce0.8O1.9-Sr2Co1.5Mo0.5O6Air electrode assembles 2032 lithium-air batteries and existed
First charge-discharge curve under 200mA/g current densities, discharge capacity reaches 3035mAh/g to battery first.
Embodiment 3：Ni-La0.8Sr0.2Ga0.85Mg0.15O3(LSGM)-Sr2Fe1.5Mo0.5O6Air electrode
Precise 12gNiO and 8gLa0.8Sr0.2Ga0.85Mg0.15O3（LSGM）It is placed in ball grinder, adds 10g diformazans
Benzene solvent, 0.5g polyvinylbutyral binders, 0.2g dibutyl phthalates and 0.3g polyethylene glycol plasticizer, 0.2g
Oleic acid dispersant and 0.2g tributyl phosphate defrothers, abundant ball milling, are made after casting slurry and curtain coating blank are made again, warp
Porous NiO-LSGM ceramic supporting bodies are made in 80 DEG C of dryings, 600 DEG C of dumpings, 1300 DEG C of sintering, and thickness is about 250 um, porosity
75%。
According to Sr2Fe1.5Mo0.5O6Stoichiometric proportion prepare the mixed solution that total concentration of metal ions is 2.0mol/L, it is former
Expect for Sr (NO3)2、Fe(NO3)3·9H2O and (NH4)6Mo7O24·4H2O.Then NiO-LSGM porous supporting bodies are impregnated above-mentioned
Mixed solution, is dried, and 2h is calcined at 600 DEG C, is taken out, then is impregnated, and is dried, calcining.So operate 3 times, be finally positioned over repeatedly
1000 DEG C of sintering 4h in Muffle furnace.Obtaining growth on skeleton has Sr2Fe1.5Mo0.5O6NiO-LSGM porous supporting bodies.
By the NiO-LSGM-Sr of preparation2Fe1.5Mo0.5O6Porous supporting body is positioned in the tube furnace for being connected with high-purity hydrogen
4h is calcined at 900 DEG C, Ni-LSGM-Sr is finally given2Fe1.5Mo0.5O6Air electrode.Sr in air electrode2Fe1.5Mo0.5O6Matter
It is 1.8% to measure fraction.
Utilize the Ni-LSGM-Sr of making2Fe1.5Mo0.5O6Air electrode, which assembles 2032 lithium-air batteries and tests battery, to be filled
Discharge performance.
Fig. 6 is to utilize Ni-LSGM-Sr2Fe1.5Mo0.5O6It is close in different electric currents that air electrode assembles 2032 lithium-air batteries
Battery first charge-discharge curve under degree, current density increases to 500 mA/g by 100, and discharge capacity of the cell is reduced only by 30%
Left and right, shows preferable high rate performance.
Embodiment 4：Ni-Gd0.2Ce0.8O1.9-Pr0.4Sr0.6Co0.2Fe0.7Nb0.1O3(PSCFN) air electrode
Precise 0.8gNiO and 0.2g Gd0.2Ce0.8O1.9It is placed in mortar, adds 0.2g starch and do pore creating material, fill
Divide grinding uniform, 3 a diameter of 12mm green compact, each green compact quality about 0.4g, then with 2 are then pressed into using tablet press machine
DEG C/min heating rate, 4h is sintered at 1200 DEG C, NiO- Gd are obtained0.2Ce0.8O1.9Porous supporting body, thickness is about
600um, porosity 50%.
According to Pr0.4Sr0.6Co0.2Fe0.7Nb0.1O3(PSCFN) stoichiometric proportion prepares total concentration of metal ions
2.0mol/L mixed solution, raw material is Pr (NO3)3·6H2O、Sr(NO3)2、Co(NO3)3·6H2O、Fe(NO3)3·9H2O and
(NH4)3[NbO(C2O4)].Then by NiO-Gd0.2Ce0.8O1.9Porous supporting body impregnates above-mentioned mixed solution, dries, at 600 DEG C
2h is calcined, is taken out, then is impregnated, is dried, calcining.So operate 3 times repeatedly, be finally positioned over 950 DEG C of sintering 6h in Muffle furnace.
Growth has Pr on to skeleton0.4Sr0.6Co0.2Fe0.7Nb0.1O3(PSCFN) NiO-Gd0.2Ce0.8O1.9Porous supporting body.
By the NiO-Gd of preparation0.2Ce0.8O1.9- PSCFN porous supporting bodies are positioned in the tube furnace for being connected with high-purity hydrogen
4h is calcined at 900 DEG C, Ni-Gd is finally given0.2Ce0.8O1.9- PSCFN air electrodes.PSCFN mass fractions are in air electrode
1.3%。
Utilize the Ni-Gd of making0.2Ce0.8O1.9- PSCFN air electrodes, which assemble 2354 lithium-air batteries and test battery, to be filled
Discharge performance.
Fig. 7 is Ni-Gd0.2Ce0.8O1.9- PSCFN air electrodes assemble 2354 lithium-air batteries in 200mA/g current densities
Under depth charging and discharging curve, as seen from the figure, through 5 circle circulation after, battery charging and discharging capacity remains at more than 50%.
Fig. 8 is Ni-Gd0.2Ce0.8O1.9The stable charge/discharge of the lithium-air battery of assembling 2354 of-PSCFN air electrodes
Test.Under conditions of being 1000mAh by capacity, after 30 circle charge and discharge cycles, the discharge voltage attenuation rate of battery is
1.2%。
Embodiment 5：Ni-La0.8Sr0.2Ga0.85Mg0.15O3(LSGM)-La0.4Sr0.6Co0.2Fe0.7Nb0.1O3 (LSCFN) it is empty
Pneumoelectric pole
Precise 12gNiO and 8gLa0.8Sr0.2Ga0.85Mg0.15O3（LSGM）It is placed in ball grinder, adds 10g diformazans
Benzene solvent, 0.5g polyvinylbutyral binders, 0.2g dibutyl phthalates and 0.3g polyethylene glycol plasticizer, 0.2g
Oleic acid dispersant and 0.2g tributyl phosphate defrothers, abundant ball milling, are made after casting slurry and curtain coating blank are made again, warp
Porous NiO-LSGM ceramic supporting bodies are made in 80 DEG C of dryings, 600 DEG C of dumpings, 1300 DEG C of sintering, and thickness is about 300 um, porosity
80%。
According to La0.4Sr0.6Co0.2Fe0.7Nb0.1O3(LSCFN) stoichiometric proportion prepares total concentration of metal ions
2.0mol/L mixed solution, raw material is La (NO3)3·6H2O、Sr(NO3)2、Co(NO3)3·6H2O、Fe(NO3)3·9H2O and
(NH4)3[NbO(C2O4)].Then above-mentioned mixed solution is added drop-wise in NiO-LSGM porous supporting bodies dropwise, dried, 600 DEG C
Lower calcining 2h, takes out, then is added dropwise, and dries, calcining.So operate 3 times repeatedly, be finally positioned over 1000 DEG C of sintering in Muffle furnace
4h.Obtaining growth on skeleton has LSCFN NiO-LSGM porous supporting bodies.
The NiO-LSGM-LSCFN porous supporting bodies of preparation are positioned in the tube furnace for be connected with high-purity hydrogen at 900 DEG C and forged
4h is burnt, Ni-LSGM-LSCFN air electrodes are finally given.Sr in air electrode2Fe1.5Mo0.5O6Mass fraction is 1.1%.
2025 lithium-air batteries are assembled using the Ni-LSGM-LSCFN air electrodes of making and test battery charging and discharging
Energy.
Fig. 9 is to assemble 2025 lithium-air batteries filling first under 200 mA/g using Ni-LSGM-LSCFN air electrodes
Discharge curve, discharge capacity reaches 2543mAh/g to battery first.
Embodiment 6： Ni-YSZ-Sr2Mg1.5Mo0.5O6Air electrode
Precise 0.8gNiO and 0.2g 8%YSZ are placed in mortar, are added 0.15g starch and are done pore creating material, fully grind
Mill is uniform, is then pressed into 3 a diameter of 12mm green compact using tablet press machine, each green compact quality about 0.4g, then with 2 DEG C/
Min heating rate, 4h is sintered at 1300 DEG C, obtains NiO-YSZ porous supporting bodies, and thickness is about 400 um, porosity
65%。
According to Sr2Mg1.5Mo0.5O6Stoichiometric proportion prepare the mixed solution that total concentration of metal ions is 2.0mol/L, it is former
Expect for Mg (NO3)2、Sr(NO3)2、Co(NO3)3·6H2O、Fe(NO3)3·9H2O and (NH4)6Mo7O24·4H2O.Then by NiO-
YSZ porous supporting bodies are impregnated in above-mentioned mixed solution, drying, are calcined 2h at 600 DEG C, are taken out, then are impregnated, and are dried, calcining.So
Operate 3 times repeatedly, be finally positioned over 950 DEG C of sintering 6h in Muffle furnace.Obtaining growth on skeleton has Sr2Mg1.5Mo0.5O6NiO-
YSZ porous supporting bodies.
By the NiO-YSZ-Sr of preparation2Mg1.5Mo0.5O6Porous supporting body is positioned over 900 in the tube furnace for be connected with high-purity hydrogen
4h is calcined at DEG C, Ni-YSZ-Sr is finally given2Mg1.5Mo0.5O6Air electrode.Sr in air electrode2Mg1.5Mo0.5O6Quality point
Number is 1.7%.
Utilize the Ni-YSZ-Sr of making2Mg1.5Mo0.5O6Air electrode, which assembles 2032 lithium-air batteries and tests battery, to be filled
Discharge performance.First discharge capacity of the battery under 200 mA/g reaches 3210mAh/g.Coulombic efficiency is 73%.
Embodiment 7： Ni-Gd0.2Ce0.8O1.9-La0.75Sr0.25Cr0.5Mn0.5O3(LSCM) air electrode
Precise 0.8gNiO and 0.2g Gd0.2Ce0.8O1.9(GDC) it is placed in mortar, adds 0.15g starch and make
Hole agent, is fully ground uniform, is then pressed into 3 a diameter of 12mm green compact using tablet press machine, each green compact quality about 0.4g,
Then with 2 DEG C/min heating rate, 4h is sintered at 1300 DEG C, NiO-GDC porous supporting bodies are obtained, thickness is about 700
Um, porosity 75%.
According to La0.75Sr0.25Cr0.5Mn0.5O3Stoichiometric proportion prepare the mixing that total concentration of metal ions is 2.0mol/L
Solution, raw material is La (NO3)3·6H2O、Sr(NO3)2、Cr(NO3)3·6H2O、Mn(NO3)2.Then by NiO-GDC open supports
Body impregnates above-mentioned mixed solution, dries, and 2h is calcined at 650 DEG C, takes out, then impregnates, and dries, calcining.So operate 6 times repeatedly,
Finally it is positioned over 900 DEG C of sintering 8h in Muffle furnace.Obtaining growth on skeleton has La0.75Sr0.25Cr0.5Mn0.5O3NiO-GDC it is many
Hole supporter.
The NiO-GDC-LSCM porous supporting bodies of preparation are positioned in the tube furnace for be connected with high-purity hydrogen at 850 DEG C and calcined
4h, finally gives Ni-GDC-LSCM air electrodes.LSCM mass fractions are 2% in air electrode.
Figure 10 is that Ni-GDC-LSCM air electrodes XRD and microscopic appearance are characterized.From XRD as can be seen that after hydrogen reducing
Ni and LSCM are chemical compatibilities, do not have side reaction；From SEM this it appears that the LSCM of generation is nano particle,
It is even to be distributed in Ni-GDC porous supporting body holes.Using the method for the present invention, catalyst raw material is easier in access aperture, is synthesized
Catalyst be evenly distributed in hole, it is uneven to overcome in existing method catalyst distribution, can only rest on supporting body surface
Defect.
2032 lithium-air batteries are assembled using the Ni-GDC-LSCM air electrodes of making and test battery charging and discharging performance.
First discharge capacity of the battery under 200 mA/g reaches 4530mAh/g.Coulombic efficiency is 75%.
Embodiment 8： Ni-YSZ-La0.8Sr0.2MnO3(LSM) air electrode
Precise 0.6gNiO and 0.4g 8mol%Y2O3-ZrO2(YSZ) it is placed in mortar, adds 0.15g starch and do
Pore creating material, is fully ground uniformly, 3 a diameter of 12mm green compact is then pressed into using tablet press machine, each green compact quality is about
0.4g, then with 1.5 DEG C/min heating rate, 4h is sintered at 1250 DEG C, obtains NiO-YSZ porous supporting bodies, thickness is about
For 450 um, porosity 75%.
According to La0.8Sr0.2MnO3Stoichiometric proportion prepare the mixed solution that total concentration of metal ions is 1.0mol/L, it is former
Expect for La (NO3)3·6H2O、Sr(NO3)2、Mn(NO3)2.Then NiO-YSZ porous supporting bodies are impregnated into above-mentioned mixed solution, dried
It is dry, 2h is calcined at 600 DEG C, is taken out, then impregnate, dry, calcining.So operate 4 times, be finally positioned over 800 in Muffle furnace repeatedly
DEG C sintering 5h.Obtaining growth on skeleton has LSM NiO-YSZ porous supporting bodies.
The NiO-YSZ-LSM porous supporting bodies of preparation are positioned in the tube furnace for be connected with high-purity hydrogen at 800 DEG C and calcined
4h, finally gives Ni-YSZ-LSM air electrodes.LSM mass fractions are 1.4% in air electrode.
2032 lithium-air batteries are assembled using the Ni-GDC-LSCM air electrodes of making and test battery charging and discharging performance.
First discharge capacity of the battery under 500 mA/g reaches 2530mAh/g.Coulombic efficiency is 72%.
Embodiment 9： Ni-CeO2-La0.6Sr0.4Co0.2Fe0.8O3Air electrode
Precise 0.7gNiO and 0.3g CeO2It is placed in mortar, adds 0.15g starch and do pore creating material, be fully ground
Uniformly, 3 a diameter of 12mm green compact, each green compact quality about 0.4g, then with 2 DEG C/min are then pressed into using tablet press machine
Heating rate, sinter 4h at 1300 DEG C, obtain NiO-CeO2Porous supporting body, thickness is about 550 um, porosity 70%.
According to La0.6Sr0.4Co0.2Fe0.8O3Stoichiometric proportion prepare the mixing that total concentration of metal ions is 2.0mol/L
Solution, raw material is La (NO3)3·6H2O、Sr(NO3)2、Co(NO3)3·6H2O、Fe(NO3)3·9H2O.Then by NiO-CeO2It is many
Hole supporter impregnates above-mentioned mixed solution, dries, and 2h is calcined at 650 DEG C, takes out, then impregnates, and dries, calcining.So grasp repeatedly
Make 5 times, be finally positioned over 900 DEG C of sintering 4h in Muffle furnace.Obtaining growth on skeleton has La0.6Sr0.4Co0.2Fe0.8O3NiO-
CeO2Porous supporting body.
By the NiO-CeO of preparation2-La0.6Sr0.4Co0.2Fe0.8O3Porous supporting body is positioned over the tubular type for being connected with high-purity hydrogen
4h is calcined at 800 DEG C in stove, Ni-CeO is finally given2-La0.6Sr0.4Co0.2Fe0.8O3Air electrode.In air electrode
La0.6Sr0.4Co0.2Fe0.8O3Mass fraction is 0.9%.
Utilize the Ni-CeO of making2-La0.6Sr0.4Co0.2Fe0.8O3Air electrode assembles 2032 lithium-air batteries and tested
Battery charging and discharging performance.First discharge capacity of the battery under 200 mA/g reaches 3517mAh/g.Coulombic efficiency is 78%.
Embodiment 10： Ni-CeO2-Ba0.5Sr0.5Co0.8Fe0.2O3Air electrode
Precise 0.8gNiO and 0.2g CeO2It is placed in mortar, adds 0.15g starch and do pore creating material, be fully ground
Uniformly, be then pressed into 3 a diameter of 12mm green compact using tablet press machine, each green compact quality about 0.4g, then with 2.2 DEG C/
Min heating rate, sinters 4h at 1350 DEG C, obtains NiO-CeO2Porous supporting body, thickness is about 700 um, porosity
78%。
According to Ba0.5Sr0.5Co0.8Fe0.2O3Stoichiometric proportion prepare the mixing that total concentration of metal ions is 2.5mol/L
Solution, raw material is Ba (NO3)2、Sr(NO3)2、Co(NO3)3·6H2O、Fe(NO3)3·9H2O.Then by NiO-CeO2Open support
Body impregnates above-mentioned mixed solution, dries, and 2h is calcined at 600 DEG C, takes out, then impregnates, and dries, calcining.So operate 3 times repeatedly,
Finally it is positioned over 850 DEG C of sintering 4h in Muffle furnace.Obtaining growth on skeleton has Ba0.5Sr0.5Co0.8Fe0.2O3NiO-CeO2It is porous
Supporter.
By the NiO-CeO of preparation2- Ba0.5Sr0.5Co0.8Fe0.2O3Porous supporting body is positioned over the tubular type for being connected with high-purity hydrogen
4h is calcined at 800 DEG C in stove, Ni-CeO is finally given2-Ba0.5Sr0.5Co0.8Fe0.2O3Air electrode.In air electrode
Ba0.5Sr0.5Co0.8Fe0.2O3Mass fraction is 1.3%.
Utilize the Ni-CeO of making2-Ba0.5Sr0.5Co0.8Fe0.2O3Air electrode assembles 2032 lithium-air batteries and tested
Battery charging and discharging performance.First discharge capacity of the battery under 200 mA/g reaches 4320mAh/g.Coulombic efficiency is 77%.
Embodiment 11： Ni-CeO2-Ba0.9Co0.7Fe0.2Nb0.1O3Air electrode
Precise 0.8gNiO and 0.2g CeO2It is placed in mortar, adds 0.15g starch and do pore creating material, be fully ground
Uniformly, 3 a diameter of 12mm green compact, each green compact quality about 0.4g, then with 2 DEG C/min are then pressed into using tablet press machine
Heating rate, sinter 4h at 1300 DEG C, obtain NiO-CeO2Porous supporting body, thickness is about 250 um, porosity 75%.
According to Ba0.9Co0.7Fe0.2Nb0.1O3(BCFNO) it is 2.0mol/L that stoichiometric proportion, which prepares total concentration of metal ions,
Mixed solution, raw material be Ba (NO3)2、Co(NO3)3·6H2O、Fe(NO3)3·9H2O and (NH4)3[NbO(C2O4)].Then will
NiO-CeO2Porous supporting body impregnates above-mentioned mixed solution, dries, and 2h is calcined at 600 DEG C, takes out, then impregnates, and dries, calcining.
So operate 5 times repeatedly, be finally positioned over 950 DEG C of sintering 6h in Muffle furnace.Obtaining growth on skeleton has
Ba0.9Co0.7Fe0.2Nb0.1O3NiO-CeO2Porous supporting body.
By the NiO-CeO of preparation2- BCFNO porous supporting bodies are positioned in the tube furnace for be connected with high-purity hydrogen at 900 DEG C
4h is calcined, Ni-CeO is finally given2- BCFNO air electrodes.Ba in air electrode0.9Co0.7Fe0.2Nb0.1O3Mass fraction is
1.5%。
Utilize the Ni-CeO of making2- BCFNO air electrodes assemble 2032 lithium-air batteries and test battery charging and discharging
Energy.First discharge capacity of the battery under 200 mA/g reaches 4210mAh/g.Coulombic efficiency is 76%, and survey is put entirely through 5 complete fill
Capability retention is more than 75% after examination.
Comparative example 1：Nickel foam-BCFNO air electrodes
0.18mol BaCO are weighed according to stoichiometric proportion3, 0.0467mol Co3O4, 0.02mol Fe2O3With
0.01mol Nb2O5It is placed in agate ball ink tank, through planetary ball mill ball milling 24h, then through tabletting machine, is then placed on case
1000 DEG C of roastings 24h, size-reduced obtained Ba in formula stove0.9Co0.7Fe0.2Nb0.1O3(BCFNO)。
According to 10:80:10 mass ratio weighs BCFNO, acetylene black and PVDF binding agents, adds appropriate nmp solvent, through super
Sound is scattered to form electrode slurry, then using spraying method is by above-mentioned electrode material but is loaded in foamed nickel current collector, vacuum
Drying is stayed overnight, and is finally carried out 2032 button lithium-air batteries of assembling and is carried out performance test.
Figure 11 is the charging and discharging curve that comparative example 1 assembles lithium-air battery.What comparative example 1 and embodiment 11 were used is all
BCFNO air electrode catalysts, but compared with embodiment 11, charging and discharging currents density is smaller in comparative example, and specific capacity is relatively low,
And capability retention is poor, under 50mA/g low current density, the capacity attenuation more than 50% after 3 discharge and recharges.
Claims (8)
1. a kind of preparation method of soap-free emulsion polymeization formulation lithium-air battery air electrode, it is characterised in that comprise the following steps：
（1）Using nickel oxide and oxygen ion conductor material as raw material, the porous nickel oxide ceramics that thickness is 200~800 microns are prepared,
The mass ratio of wherein nickel oxide and oxygen ion conductor material is（1~4）∶1；
（2）The raw material for preparing lithium-air battery air electrode catalyst is added to the water, solution is configured to；The lithium-air electricity
Pond air electrode catalyst is perovskite oxide；The metal ion in solution total concentration is 0.2~2mol/L；The lithium-
Air cell air electrode catalyst is Ba0.9Co0.7Fe0.2Nb0.1O3、La0.8Sr0.2MnO3、La0.6Sr0.4Co0.2Fe0.8O3、
Ba0.5Sr0.5Co0.8Fe0.2O3、La0.75Sr0.25Cr0.5Mn0.5O3、Ln0.4Sr0.6Co0.2Fe0.7Nb0.1O3Or Sr2M2-xMoxO6；Its
Middle Ln is La, Pr or Sm；M is Fe, Co, Cr, Mg or Mn；
（3）By solution described in the porous nickel oxide cerdip, take out and calcined after drying, last sintered processing is supported
The porous nickel oxide ceramics of lithium-air battery air electrode catalyst；
（4）The porous nickel oxide ceramics for supporting lithium-air battery air electrode catalyst pass through hydrogen or argon hydrogen gaseous mixture
Soap-free emulsion polymeization formulation lithium-air battery air electrode is obtained after body annealing.
2. the preparation method of soap-free emulsion polymeization formulation lithium-air battery air electrode according to claim 1, it is characterised in that：Step
Suddenly（1）In, after nickel oxide and oxygen ion conductor material are mixed, green compact, green compact warp are prepared using Mechanical pressing method or the tape casting
Porous nickel oxide ceramics are obtained after sintering.
3. the preparation method of soap-free emulsion polymeization formulation lithium-air battery air electrode according to claim 2, it is characterised in that：Adopt
When preparing green compact with Mechanical pressing method, using graphite or starch as pore creating material；When preparing green compact using the tape casting, using dimethylbenzene as
Solvent, polyvinyl butyral resin is binding agent, and dibutyl phthalate and polyethylene glycol are plasticizer, and oleic acid is dispersant,
Tributyl phosphate is defrother.
4. the preparation method of soap-free emulsion polymeization formulation lithium-air battery air electrode according to claim 1, it is characterised in that：
Step（1）In, the oxygen ion conductor material is CeO2、Sm0.2Ce0.8O1.9、Gd0.2Ce0.8O1.9、
La0.8Sr0.2Ga0.85Mg0.15O3Or 8 mol%Y2O3-ZrO2。
5. the preparation method of soap-free emulsion polymeization formulation lithium-air battery air electrode according to claim 1, it is characterised in that：Step
Suddenly（3）In, by solution described in the porous nickel oxide cerdip, take out and calcined after drying；Then by the porous oxygen after calcining
Change nickel ceramics to continue to impregnate the solution, take out and calcined after drying；Repeat 3~6 times；Finally sintered processing is supported again
The porous nickel oxide ceramics of lithium-air battery air electrode catalyst.
6. the preparation method of soap-free emulsion polymeization formulation lithium-air battery air electrode according to claim 1, it is characterised in that：Step
Suddenly（3）In, the calcining is calcined 2 hours for 600~650 DEG C；The sintering processes are 900~1000 DEG C and sintered 4~8 hours；
Step（4）In, the annealing is handled 4 hours for 800~950 DEG C.
7. according to claim 1~6 any one prepared by the preparation method of soap-free emulsion polymeization formulation lithium-air battery air electrode
Soap-free emulsion polymeization formulation lithium-air battery air electrode, it is characterised in that：The soap-free emulsion polymeization formulation lithium-air battery air electrode
By porous nickel metal ceramics and support in the porous nickel metal ceramics on lithium-air battery air electrode catalyst group
Into；In the soap-free emulsion polymeization formulation lithium-air battery air electrode, the mass fraction of catalyst is 0.2~2%；The porous nickel gold
The porosity of category ceramics is 40~80%.
8. application of the soap-free emulsion polymeization formulation lithium-air battery air electrode in lithium-air battery is prepared described in claim 7.
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