CN106099127A - Preparation method of air electrode catalyst of lithium-air battery - Google Patents
Preparation method of air electrode catalyst of lithium-air battery Download PDFInfo
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- CN106099127A CN106099127A CN201610517499.2A CN201610517499A CN106099127A CN 106099127 A CN106099127 A CN 106099127A CN 201610517499 A CN201610517499 A CN 201610517499A CN 106099127 A CN106099127 A CN 106099127A
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- lithium
- air battery
- perovskite oxide
- battery
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inert Electrodes (AREA)
Abstract
The invention provides a preparation method of a lithium-air battery air electrode catalyst, which comprises the following steps: synthesizing monodisperse SiO with mesoporous structure on surface2Microspheres; making monodisperse SiO by vertical deposition2Self-assembly of microspheres into three-dimensional ordered SiO2A colloidal crystal template; filling the metal salt precursor of perovskite oxide into the pores of the colloidal crystal by pore infiltration methodDrying and sintering the perovskite oxide in the gaps to crystallize the perovskite oxide; soaking the material obtained in S3 in NaOH to remove SiO2Obtaining perovskite oxide with a three-dimensional ordered macroporous structure by using a template; characterizing the physical and chemical properties of the perovskite oxide catalyst material with the three-dimensional ordered macroporous/mesoporous composite structure; and assembling the lithium-air battery into a button lithium-air battery, and characterizing the charge-discharge capacity, the coulombic efficiency, the cycle performance and the rate performance of the lithium-air battery. The polarization of the battery can be reduced, the charge and discharge efficiency of the battery can be improved, and the cycle life of the lithium air battery can be prolonged.
Description
Technical field
The present invention relates to lithium-air battery electrode material development technique field, particularly relate to a kind of lithium-air battery air electricity
The preparation method of electrode catalyst.
Background technology
Lithium-air battery has higher theoretical specific energy, and when using organic bath, its theoretical specific energy can reach
To 3622Wh/kg, almost with being on close level, far above the level of current lithium ion battery 100～120Wh/kg of fuel oil.But
It is that in actual applications, lithium-air battery existence charging polarization is big, efficiency for charge-discharge is low, cycle life is short, high rate performance is poor
Problem.For the air electrode of lithium-air battery, how to obtain the catalysis that hydrogen reduction/evolution reaction is had effective catalytic action
Agent, thus improve the direction that the performance of battery, always researchers are continually striving to.The reduction of oxygen electrode/evolution reaction is simultaneously
Relate to gas-liquid-solid phase reaction interface, how to increase three phase boundary length, be the key improving catalyst performance.This
Outward, research shows, lithium-air battery based on organic electrolyte system, and the core of its battery chemistries reaction is Li2O2Reversible
Generate and decompose.Due to Li2O2Electric conductivity is very poor, must have enough spaces to accommodate discharging product Li in electrode2O2, prevent
Due to Li2O2Electrode is coated with completely and causes discharge off.Based on above analysis, lithium-air battery air electrode catalyst
Microstructure, it is necessary to meet simultaneously following of both require: (1) has high specific surface area, to provide sufficient reaction
Avtive spot, improves the catalysis activity of catalyst；(2) there is higher porosity and enough apertures such that it is able to accommodate more
Many product Li2O2, extend the cycle life of battery.
Improve the activity of catalyst by changing the microstructure of air electrode, researchers have been carried out
Some are attempted.In research in recent years, catalyst is prepared as special nanostructured, such as nanotube, nanometer by people
Rod, hollow nanosphere etc., by the nanorize of electrode to improve the discharge capacity of lithium-air battery.Research shows, air electrode
The discharge performance of battery is had a great impact by the factors such as the pattern of inside, aperture, pore volume, specific surface area, thickness of electrode.Electricity
The surface pore of tankage and electrode, especially average pore size is closely related with pore volume, along with average pore size and pore volume
Increasing, discharge time and specific capacity increase therewith.However, it is contemplated that simultaneously need to higher specific surface area and sufficient aperture/
Pore volume, single aperture structure is difficult to meet requirement, and having that the combination of mesoporous material and large pore material is formed is multistage
The catalyst of pore passage structure, it should requirements above can be met well.
Analyze based on above, the present invention relates to a kind of Perovskite Catalytic with three-dimensional ordered macroporous/composite mesoporous structure
Agent, and apply it in lithium-air battery.It is expected that by the structure of this three-dimensional ordered macroporous/composite mesoporous structure catalyst
Build, reduce the polarization of charge and discharge process, improve the discharge capacity of lithium-air battery, promote the discharge and recharge conversion of lithium-air battery
Efficiency, improves the cycle performance of secondary lithium-air battery.
Summary of the invention
For solving above-mentioned technical problem, the invention provides the preparation side of a kind of air electrode for lithium air battery catalyst
Method, compared with normal granular catalyst, meso-hole structure can increasing specific surface area, increase catalytic reaction activity position；Macropore is tied
Structure can provide receiving discharging product Li2O2Space；The transmission of DC channel, beneficially electronics of nanotube morphogenesis.Tool
There is the catalyst of this structure, it is possible to reduce battery polarization, improve the efficiency for charge-discharge of battery, extend the circulation of lithium-air battery
Life-span.
The technical solution adopted in the present invention is: the preparation method of a kind of air electrode for lithium air battery catalyst, including
Following steps:
S1, synthetic surface have meso-hole structure, monodispersed SiO2Microsphere；
S2, make monodispersed SiO by vertical deposition method2Microsphere is self-assembled into the SiO of three-dimensional order2Colloidal crystal template；
S3, by hole soaking method, the slaine presoma of perovskite oxide is filled in the hole of colloidal crystal, warp
Cross be dried, sintering make perovskite oxide crystallize；
S4, the material obtained by S3 soak removal SiO in NaOH2Template, obtains having three-dimensional ordered macroporous structure
Perovskite oxide, and, due to SiO2There is meso-hole structure in microsphere surface, also same on the three-dimensional ordered macroporous hole wall obtained
Sample has meso-hole structure；
S5, physicochemical properties to the perovskite oxide catalyst material of three-dimensional ordered macroporous/composite mesoporous structure
Characterize；
S6, it is assembled into button lithium-air battery, its charge/discharge capacity, coulombic efficiency, cycle performance and high rate performance are entered
Row characterizes.
The one or more technical schemes provided in the embodiment of the present application, at least have the following technical effect that or advantage:
For lithium-air battery, by the introducing of perovskite bi-functional oxygen electrode catalyst, reduce the polarization of reaction, fall
The charging voltage of low battery, and then improve the charge/discharge capacity of lithium-air battery, extend the circulation longevity of secondary lithium-air battery
Life.
Surface is used to have the single dispersing SiO of meso-hole structure2Microsphere is as template, and preparation has three-dimensional ordered macroporous/Jie
The perovskite oxide of hole composite construction.Wherein, meso-hole structure has the specific surface area of superelevation, using the teaching of the invention it is possible to provide more react alive
Property position, and the hole of more receiving discharging product is provided；The introducing of macropore is more beneficial for the quick transmission of gas, and provides more
Accommodate the hole of discharging product, thus improve cycle performance and the high rate performance of lithium-air battery further.
Detailed description of the invention
In order to be better understood from technique scheme, will in particular embodiments technique scheme be carried out in detail below
Thin explanation.
The preparation method of a kind of air electrode for lithium air battery catalyst described in the present embodiment, specifically comprises the following steps that
1, monodisperse mesoporous SiO2Synthesis: by the cetyl trimethylammonium bromide (CTAB) of 0.003-0.01mol/L
It is dissolved in deionized water, adds ethanol in proper amount (V ethanol/V water is 0-20%) and the sodium hydroxide of 0.01-0.03mo1/L, 80
It is stirred vigorously at a temperature of degree to solution clear, is under agitation rapidly added the tetraethyl orthosilicate of 0.02-0.1mo1/L
(TEOS), continue to be stirred vigorously 2 hours, following reaction mixture sequentially pass through filtration, washing with alcohol three times, at a temperature of 60 degree
It is vacuum dried 12 hours, is calcined 5 hours at a temperature of 550 degree, i.e. obtain sphericity mesoporous silicon dioxide nano material.
2, by vertical deposition method by monodispersed SiO2Microsphere is assembled into SiO2Colloidal crystal template: be with deionized water
Disperse medium, be situated between SiO by single dispersing2Powder body ultrasonic disperse in deionized water, is configured to the PS that concentration is 0.1%-0.7% and divides
Dissipate liquid.The PS emulsion of 10ml is placed in 20ml small beaker, the matrix of ultrasonic cleaning is vertically fixed in small beaker, by little
Beaker is placed in the baking oven of 25-55 degree, allow PS granule in the case of without external disturbance, in matrix surface generation self assembly
Obtain colloidal crystal.
3, the filling of perovskite oxide presoma: by hole soaking method by the metal nitrate salt precursor of perovskite oxide
Body is filled in the hole of colloidal crystal.First, configuration concentration is the perovskite oxide presoma La1-of 0.1-0.5mo1/L
xSrxM(NO3)3(M=Co, Mn, Fe, 0 < X < 0.5)；Then, SiO2 colloidal crystal template is vertically impregnated into precursor sol liquid
In, standing 1～2min, precursor sol thing enters in the gap of SiO2 colloidal spheres under the effect of capillary force；Subsequently, will fill out
Substitute the bad for the good the SiO of colloidal sol2Template vertically slowly lifts out with the speed of 2mm/s from colloidal sol, is dried at room temperature for.Impregnate-carry
The process drawn can repeat 1-5 time.
4, the sintering of perovskite oxide: the material (3) obtained sinters 2-6h under 750-900 degree, makes in presoma
Organic substance decompose, perovskite oxide crystallize, obtain La1-xSrxMO3(M=Co, Mn, Fe, 0 < X < 0.5).
5、SiO2The removal of colloidal crystal template: under 25-80 degree, the perovskite oxide shell by Surface coating
SiO2It is immersed in the NaOH solution of 10-50wt% 3-5 days, to remove SiO2Template, finally give have three-dimensional ordered macroporous/
The perovskite oxide catalyst of meso-hole structure.
6, the final catalyst obtained is carried out X-ray diffraction (XRD), scanning electron microscope (SEM), projection electron
Microscope (TEM), N2 adsorption desorption isotherm and pore-size distribution test, characterize three-dimensional ordered macroporous and mesoporous pattern.
7, by obtain, there is the catalyst of three-dimensional ordered macroporous/meso-hole structure, carbonaceous conductive agent and Kynoar
(PVDF) binding agent mixes according to the ratio of 1: 2: 0.5, adds appropriate solvent N-methyl pyrilidone (NMP) and is stirred obtaining
Slurry.Slurry is coated on carbon paper, is vacuum dried 8～12h at 80-120 degree.Dried pole piece is cut into diameter 14mm
Disk, i.e. obtain the air electrode of lithium-air battery.The carrying capacity of catalyst is 0.1-0.5mg cm-2。
8, with the metal lithium sheet of diameter 15.6mm as negative pole, the celgard2400 isolating membrane of diameter 18mm, 1mol/L are used
LiTFSi (double trifluoromethanesulfonimide lithium)/TEGDME (TRIGLYME) electrolyte, in glove box assemble
2032 button lithium-air batteries, and its charge-discharge performance is characterized.Discharge and recharge blanking voltage is 2.0-4.6V, electric current density
For 0.1mA cm-2。
The above, be only presently preferred embodiments of the present invention, and the present invention not makees any pro forma restriction, though
So the present invention is disclosed above with preferred embodiment, but is not limited to the present invention, any technology people being familiar with this specialty
Member, in the range of without departing from technical solution of the present invention, when the technology contents of available the disclosure above makes a little change or modification
For the Equivalent embodiments of equivalent variations, as long as being the content without departing from technical solution of the present invention, the technical spirit of the foundation present invention
Any simple modification, equivalent variations and the modification being made above example, all still falls within the range of technical solution of the present invention.
Claims (1)
1. the preparation method of an air electrode for lithium air battery catalyst, it is characterised in that comprise the following steps:
S1, synthetic surface have meso-hole structure, monodispersed SiO2 microsphere；
S2, monodispersed SiO2 microsphere is made to be self-assembled into the SiO2 colloidal crystal template of three-dimensional order by vertical deposition method；
S3, by hole soaking method, the slaine presoma of perovskite oxide is filled in the hole of colloidal crystal, through overdrying
Dry, sintering makes perovskite oxide crystallize；
S4, the material obtained by S3 soak removal SiO2 template in NaOH, obtain the calcium titanium with three-dimensional ordered macroporous structure
Ore deposit oxide, and, owing to SiO2 microsphere surface exists meso-hole structure, the three-dimensional ordered macroporous hole wall obtained has too
There is meso-hole structure；
S5, physicochemical properties to the perovskite oxide catalyst material of three-dimensional ordered macroporous/composite mesoporous structure are carried out
Characterize；
S6, it is assembled into button lithium-air battery, its charge/discharge capacity, coulombic efficiency, cycle performance and high rate performance are carried out table
Levy.
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| CN201610517499.2A CN106099127A (en) | 2016-07-04 | 2016-07-04 | Preparation method of air electrode catalyst of lithium-air battery |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109888315A (en) * | 2019-03-21 | 2019-06-14 | 深圳先进技术研究院 | A kind of processing method promoting B doping type perovskite catalyst chemical properties |
-
2016
- 2016-07-04 CN CN201610517499.2A patent/CN106099127A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109888315A (en) * | 2019-03-21 | 2019-06-14 | 深圳先进技术研究院 | A kind of processing method promoting B doping type perovskite catalyst chemical properties |
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Application publication date: 20161109 |