CN107195915B - A kind of lithium air battery positive electrode catalyst material, lithium air battery positive electrode and preparation method thereof - Google Patents
A kind of lithium air battery positive electrode catalyst material, lithium air battery positive electrode and preparation method thereof Download PDFInfo
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- CN107195915B CN107195915B CN201710413853.1A CN201710413853A CN107195915B CN 107195915 B CN107195915 B CN 107195915B CN 201710413853 A CN201710413853 A CN 201710413853A CN 107195915 B CN107195915 B CN 107195915B
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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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
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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
- H01M4/88—Processes of manufacture
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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
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8828—Coating with slurry or ink
- H01M4/8839—Painting
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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
- H01M4/9091—Unsupported catalytic particles; loose particulate catalytic materials, e.g. in fluidised state
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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
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8689—Positive electrodes
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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
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to field of chemical power source more particularly to a kind of lithium air battery positive electrode catalyst material, lithium air battery positive electrode and preparation method thereof.The anode catalytic agent material is the Mo with rutile structurexOyMaterial, MoxOyMaterial is MoO2And Mo17O47One or both of mixture, MoO2And Mo17O47Mixture in MoO2And Mo17O47Mass ratio be 1:1-1:3, MoO2Powder is prepared by reduction method, Mo17O47Powder is prepared by chemical vapour deposition technique.Lithium air battery positive electrode catalyst is prepared using cladding process, by positive carbon material and MoxOyMaterial is mixed to get positive electrode in 5:5 or 7:3 or 8:2 ratio；By mass ratio be 7:3 or 8:2 positive electrode and after bonding agent ultrasound 20-30 minute be uniformly mixed and apply on a current collector, at 100-120 DEG C dry 10-12h after obtain lithium air battery positive electrode.Mo using rutile structure of the inventionxOyMaterial does the lithium-air battery of anode catalyst, lithium ion and electronics insertion abjection diffusion admittance it is more, apart from short, speed is fast, effectively improve the chemical property of battery.
Description
Technical field
The present invention relates to field of chemical power source more particularly to a kind of lithium air battery positive electrode catalyst materials, lithium air electricity
Pond anode and preparation method thereof.
Background technique
Metal-air battery is one of the representative of new generation of green secondary cell, has at low cost, nontoxic, pollution-free, ratio
The advantage that power is high, specific energy is high, wherein the theoretical specific energy of lithium-air battery be it is highest in the reversible power supply of chemistry, comparable to
Gasoline, its is environmental-friendly, low in cost in addition, has caused highest attention in global field of chemical power source.Lithium-air battery according to
Electrolyte system is different, can be divided into 4 kinds of organic system, water system, mixed system and all solid state electrolyte systems, and 1996,
After Abraham and Jiang proposes the concept of non-aqueous lithium air cell, the fatal defects of aqueous lithium-air battery are overcome, are made
It, which is studied, enters the new stage.Non-aqueous lithium air cell is by lithium (or lithium alloy) piece cathode, air cathode, diaphragm and non-aqueous
Electrolyte composition, wherein positive active material is derived from the oxygen in atmosphere, and negative metal lithium possesses oxidation most negative in nature
It restores equilibrium potential (E °=- 3.01V vs.SHE), therefore the theoretical energy density of battery is up to 11680Wh/kg.Non-aqueous lithium
Air cell during discharge, the only absorption and release of oxygen, referred to as " respirable battery ".Therefore, either from
The energy still from an environmental point of view, all has very important strategic importance to the exploration of high-energy lithium-air battery, and
Huge economical, societal benefits may be brought in future.
Currently, the research of non-aqueous lithium oxygen cell is in laboratory stage, most of research of lithium-air battery is pure
It is carried out under the conditions of oxygen, practical application then needs to carry out in atmospheric conditions, and partial pressure of oxygen will be by PO2>=1atm is down to
The output energy of 0.21atm, battery can also significantly reduce, and the oxygen transmission performance and kinetics performance of battery also can be significant
It reduces, therefore finding a kind of suitable catalyst to increase dynamics of oxidation-reduction is that current lithium-air battery field will solve
One of the technical issues of.
Summary of the invention
The object of the present invention is to provide the lithium-air battery catalysis that a kind of low-resistivity, high electrochemical activity, performance are stable
The lithium air battery positive electrode and preparation method thereof of agent material and the application catalyst material.
The technical solution of the present invention is as follows: a kind of lithium air battery positive electrode catalyst material, the anode catalytic agent material are
MoxOyMaterial, the MoxOyMaterial has rutile structure, the MoxOyMaterial is MoO2And Mo17O47One or both of
Mixture；
MoO2And Mo17O47Mixture in MoO2And Mo17O47Mass ratio be 1:1-1:3.
Further, MoO2Material is prepared by reduction method, preparation method are as follows: (1) by silester and hydrophilic fumed silica
It is mixed in a certain ratio, pours into the mixed solution of second alcohol and water, stand 20-24h, calcine 3-5h at 600-700 DEG C, obtain
Make SiO by oneself2Template；(2) by a certain amount of (NH4)6Mo7O24It is dissolved in deionized water, self-control SiO is added in whipping process2Template,
DEG C heating removal deionized water, obtains white powder under 60~70；(3) by the white powder in step (2) at 600-700 DEG C
Temperature, H26-7h is calcined under reducing atmosphere；(4) it will take out, be added through the calcined powder of reducing atmosphere in step (3)
1.8-2.4MHF removing self-control SiO2Template obtains MoO2Powder.
Further, the mixing ratio of silester and hydrophilic fumed silica is 5:5 or 7:3 in step (1)；The mixing of second alcohol and water
Than for 6:4 or 8:2.
Further, Mo17O47Material is prepared by chemical vapour deposition technique, preparation method are as follows: (1) in CVD device
A certain amount of Mo powder is added, keeping central temperature is 760-780 DEG C；(2) when oxygen pressure is 1.1-1.2Torr, with 0.05-
0.06m3The speed of/h is passed through oxygen, reacts 30-35min, obtains Mo17O47Powder.
A kind of lithium air battery positive electrode, including above-mentioned lithium air battery positive electrode catalyst material.
A kind of preparation method of lithium air battery positive electrode, is prepared using cladding process, includes the following steps: (1) by positive carbon
Material and MoxOyMaterial is mixed to get positive electrode in 5:5 or 7:3 or 8:2 ratio；(2) positive electrode and bonding agent are pressed into 7:3
Or the mass ratio ultrasound of 8:2 is uniformly mixed after 20-30 minutes；(3) the good mixture of ultrasound in step (2) is coated in afflux
On body, lithium air battery positive electrode is obtained after dry 10-12h at 100-120 DEG C.
Further, the carbon material used in step (1) is one of Super P, carbon nanotube, graphene.
Further, the bonding agent in step (2) is one of PVDF, LA132, SBR+CMC, polyvinyl alcohol.
Further, the collector in step (3) is copper mesh or nickel foam, and the diameter of the collector is 12-16mm.
The invention has the following advantages:
(1) the anode catalytic agent material of lithium-air battery of the invention, has rutile structure, and large specific surface area is conductive
Effect is good, and reduction method can be used or chemical vapour deposition technique is made, preparation method is simple, process costs are low, catalytic effect is significant；
(2) the lithium air battery positive electrode catalyst with rutile structure of the invention, improves putting for lithium-air battery
Capacitance improves discharge voltage plateau, excellent catalytic effect；
(3) lithium air battery positive electrode of the invention, lithium ion and electronics insertion abjection diffusion admittance it is more, apart from short, speed
Fastly, the chemical property of battery is effectively improved.
Detailed description of the invention
Illustrate the embodiment of the present invention or technical solution in the prior art in order to clearer, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it is clear that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
Other attached drawings are obtained according to these attached drawings.
Fig. 1 is that embodiment 3 and X-ray diffraction (XRD) map of lithium air battery positive electrode in comparative example 1 compare in the present invention
Figure；
Fig. 2 is to mix MoO in the present invention2The scanning electron microscope (SEM) photograph of the lithium air battery positive electrode of anode catalytic agent material；
Fig. 3 is the discharge curve comparison diagram of embodiment 3 and lithium-air battery in comparative example 1 in the present invention；
Fig. 4 is that embodiment 4 and X-ray diffraction (XRD) map of lithium air battery positive electrode in comparative example 1 compare in the present invention
Figure；
Fig. 5 is to mix Mo in the present invention17O47The scanning electron microscope (SEM) photograph of the lithium air battery positive electrode of anode catalytic agent material；
Fig. 6 is the discharge curve comparison diagram of embodiment 4 and lithium-air battery in comparative example 1 in the present invention；
Fig. 7 is the discharge curve comparison diagram of embodiment 5 and lithium-air battery in comparative example 1 in the present invention；
Fig. 8 is the discharge curve comparison diagram of embodiment 6 and lithium-air battery in comparative example 1 in the present invention；
Fig. 9 is the discharge curve comparison diagram of embodiment 7 and lithium-air battery in comparative example 1 in the present invention；
Figure 10 is the discharge curve of embodiment 3 in the present invention, embodiment 4 and lithium-air battery in comparative example 1, comparative example 2
Comparison diagram.
Specific embodiment
Below in conjunction with the attached drawing in the present invention, technical solution in the embodiment of the present invention carry out it is clear, completely retouch
It states, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on the present invention
In embodiment, those skilled in the art's all other reality obtained without making creative work
Example is applied, protection scope of the present invention is belonged to.
A kind of lithium air battery positive electrode catalyst material of the invention, for the Mo with rutile structurexOyMaterial, should
MoxOyMaterial is MoO2And Mo17O47One or both of mixture, and MoO2And Mo17O47Mixture in MoO2And Mo17O47
Ratio be 1:1-1:3.Rutile is AB2Type ionic crystals belongs to tetragonal crystal system, and wherein anion B makees approximate hexagonal closs packing,
Cation A is filled in the half in the octahedral interstices being made of anion, contacts between A-B for ionic bond.With rutile
The Mo of structurexOyMaterial specific surface area is big, conductive effect is good, as the anode catalyst of lithium-air battery, improves lithium sky
The discharge capacity in pneumoelectric pond, improves discharge voltage plateau, and catalytic effect is significant.
Specifically, MoO2Powder is prepared by reduction method, preparation method are as follows: (1) press silester and hydrophilic fumed silica
Certain proportion mixing, is poured into the mixed solution of second alcohol and water, is stood 20-24h, is calcined 3-5h at 600-700 DEG C, is obtained certainly
SiO processed2Template；(2) by a certain amount of (NH4)6Mo7O24It is dissolved in deionized water, self-control SiO is added in whipping process2Template, In
60~70 lower DEG C of heating remove deionized water, obtain white powder；(3) by the white powder in step (2) in 600-700 DEG C of temperature
Degree, H26-7h is calcined under reducing atmosphere；(4) it will be taken out in step (3) through the calcined powder of reducing atmosphere, 1.8- be added
2.4M HF removes self-control SiO2Template obtains MoO2Powder.
Preferably, the mixing ratio of silester and hydrophilic fumed silica is 5:5 or 7:3 in step (1)；The mixing ratio of second alcohol and water
For 6:4 or 8:2.
Specifically, Mo17O47Powder is prepared by chemical vapour deposition technique, preparation method are as follows: (1) is added in CVD device
Enter a certain amount of Mo powder, keeping central temperature is 760-780 DEG C；(2) when oxygen pressure is 1.1-1.2Torr, with 0.05-
0.06m3The speed of/h is passed through oxygen, reacts 30-35min, obtains Mo17O47Powder.Wherein, the amount of Mo powder according to preparation facilities not
With and difference.
A kind of lithium air battery positive electrode of the invention, including the lithium air battery positive electrode catalyst mentioned in the embodiment of top
Material, the lithium-air battery are prepared using cladding process, comprising the following steps: (1) by positive carbon material and MoxOyMaterial by 5:5 or
7:3 or 8:2 ratio is mixed to get positive electrode；(2) positive electrode and bonding agent ultrasound 20- for being 7:3 or 8:2 by mass ratio
It is uniformly mixed after 30 minutes；(3) on a current collector by the good mixture coating of ultrasound in step (2), dry at 100-120 DEG C
Lithium air battery positive electrode is obtained after 10-12h.
Preferably, the carbon material used in step (1) is one of Super P, carbon nanotube, graphene.
Preferably, the bonding agent in step (2) is one of PVDF, LA132SBR+CMC, polyvinyl alcohol.
Preferably, the collector in step (3) is copper mesh or nickel foam, and the diameter of the collector is 12-16mm.
Mo using rutile structure of the inventionxOyMaterial does the lithium air battery positive electrode of anode catalytic agent material, lithium from
Son and electronics insertion abjection diffusion admittance it is more, apart from short, speed is fast, effectively improve the chemical property of battery.
Assemble non-aqueous lithium air cell using lithium air battery positive electrode of the invention, the battery include lithium anode,
Nonaqueous electrolyte, diaphragm and porous anode, wherein cell assembling processes carry out in the glove box full of argon gas.It is preferred that
, when assembled battery, the lithium piece that uses is is commercialized lithium piece, diameter 16mm, with a thickness of 0.3mm；Electrolyte is having for lithium salts
Machine solution, solute are double trifluoromethanesulfonimide lithiums (LITFSI), and solvent is tetraethyleneglycol dimethyl ether (TEGDME)；Diaphragm is
It is commercialized glass fiber filter paper.
Above content be described in detail lithium air battery positive electrode catalyst material of the invention, lithium air battery positive electrode and its
Preparation method will enumerate specific embodiment below and the present invention will be further described:
Embodiment 1
The MoO with rutile structure in the present embodiment2Anode catalytic agent material, is prepared using reduction method, specific side
Method is as follows:
(1) mixing that silester and hydrophilic fumed silica are pressed to 5:5, pours into the mixed solution for the second alcohol and water that ratio is 8:2
In, it stands for 24 hours, calcines 5h at 600 DEG C, obtain self-control SiO2Template；
(2) by 5g (NH4)6Mo7O24It is dissolved in 35mL deionized water, 3g is added in whipping process and makes SiO by oneself2Template, 70
Lower DEG C of heating removes deionized water, obtains white powder；
(3) by the white powder in step (2) in 650 DEG C of temperature, H26h is calcined under reducing atmosphere；
(4) it will be taken out in step (3) through the calcined powder of reducing atmosphere, 2M HF be added and removes self-control SiO2Template,
Obtain MoO2Powder.
Embodiment 2
The Mo with rutile structure in the present embodiment17O47Anode catalytic agent material, using chemical vapour deposition technique system
Standby, the specific method is as follows:
(1) a certain amount of Mo powder is added in CVD device, keeping central temperature is 760 DEG C；
(2) when oxygen pressure is 1.1Torr, with 0.05m3The speed of/h is passed through oxygen, reacts 30min, obtains Mo17O47
Powder.
Embodiment 3
The preparation of lithium air battery positive electrode:
(1) anode carbon material Super P and MoO2Material is mixed to get positive electrode in 8:2 ratio；
(2) positive electrode and bonding agent mass ratio are 7:3, and positive electrode is added in a small beaker, adds second
Alcohol simultaneously ultrasonic mixing 20 minutes, bonding agent then is added by the way of being added dropwise, is sufficiently mixed bonding agent with positive electrode, obtains
To anode sizing agent；
(3) anode sizing agent is coated on collector, it is positive to get arriving in 120 DEG C of vacuum drying 12h.
The assembling of lithium-air battery:
Being assembled in the glove box full of Ar for battery carries out, and the positive electrode of just extremely above-mentioned preparation, diaphragm is glass
Fiber filter paper, electrolyte are the TEGDME solution of 0.65mol/L LiTFSI, and cathode is the metal lithium sheet of diameter 16mm.Exist first
Battery pedestal puts down lithium piece, in placing diaphragm in lithium piece, electrolyte is then added dropwise and is put into anode.The battery standing that will be assembled
8h makes electrolyte sufficiently infiltrate anode, stands 4h again after being passed through oxygen.
Embodiment 4
The preparation of lithium air battery positive electrode:
(1) anode carbon material Super P and Mo17O47Material is mixed to get positive electrode in 8:2 ratio；
(2) positive electrode and bonding agent mass ratio are 7:3, and positive electrode is added in a small beaker, adds second
Alcohol simultaneously ultrasonic mixing 20 minutes, bonding agent then is added by the way of being added dropwise, is sufficiently mixed bonding agent with positive electrode, obtains
To anode sizing agent；
(3) anode sizing agent is coated on collector, it is positive to get arriving in 120 DEG C of vacuum drying 12h.
The assembling of lithium-air battery:
Being assembled in the glove box full of Ar for battery carries out, and the positive electrode of just extremely above-mentioned preparation, diaphragm is glass
Fiber filter paper, electrolyte are the TEGDME solution of 0.65mol/L LiTFSI, and cathode is the metal lithium sheet of diameter 16mm.Exist first
Battery pedestal puts down lithium piece, in placing diaphragm in lithium piece, electrolyte is then added dropwise and is put into anode.The battery standing that will be assembled
8h makes electrolyte sufficiently infiltrate anode, stands 4h again after being passed through oxygen.
Embodiment 5
The preparation of lithium air battery positive electrode:
(1) anode catalytic agent material MoO2With Mo17O47The mixing of 1:1 in mass ratio, positive carbon material Super P and MoO2/
Mo17O47Mixing material is mixed to get positive electrode in 8:2 ratio；
(2) positive electrode and bonding agent mass ratio are 7:3, and positive electrode is added in a small beaker, adds second
Alcohol simultaneously ultrasonic mixing 20 minutes, bonding agent then is added by the way of being added dropwise, is sufficiently mixed bonding agent with positive electrode, obtains
To anode sizing agent；
(3) anode sizing agent is coated on collector, it is positive to get arriving in 120 DEG C of vacuum drying 12h.
The assembling of lithium-air battery:
Being assembled in the glove box full of Ar for battery carries out, and the positive electrode of just extremely above-mentioned preparation, diaphragm is glass
Fiber filter paper, electrolyte are the TEGDME solution of 0.65mol/L LiTFSI, and cathode is the metal lithium sheet of diameter 16mm.Exist first
Battery pedestal puts down lithium piece, in placing diaphragm in lithium piece, electrolyte is then added dropwise and is put into anode.The battery standing that will be assembled
8h makes electrolyte sufficiently infiltrate anode, stands 4h again after being passed through oxygen.
Embodiment 6
The preparation of lithium air battery positive electrode:
(1) anode catalytic agent material MoO2With Mo17O47The mixing of 1:2 in mass ratio, positive carbon material Super P and MoO2/
Mo17O47Mixing material is mixed to get positive electrode in 8:2 ratio；
(2) positive electrode and bonding agent mass ratio are 7:3, and positive electrode is added in a small beaker, adds second
Alcohol simultaneously ultrasonic mixing 20 minutes, bonding agent then is added by the way of being added dropwise, is sufficiently mixed bonding agent with positive electrode, obtains
To anode sizing agent；
(3) anode sizing agent is coated on collector, it is positive to get arriving in 120 DEG C of vacuum drying 12h.
The assembling of lithium-air battery:
Being assembled in the glove box full of Ar for battery carries out, and the positive electrode of just extremely above-mentioned preparation, diaphragm is glass
Fiber filter paper, electrolyte are the TEGDME solution of 0.65mol/L LiTFSI, and cathode is the metal lithium sheet of diameter 16mm.Exist first
Battery pedestal puts down lithium piece, in placing diaphragm in lithium piece, electrolyte is then added dropwise and is put into anode.The battery standing that will be assembled
8h makes electrolyte sufficiently infiltrate anode, stands 4h again after being passed through oxygen.
Embodiment 7
The preparation of lithium air battery positive electrode:
(1) anode catalytic agent material MoO2With Mo17O47The mixing of 1:3 in mass ratio, positive carbon material Super P and MoO2/
Mo17O47Mixing material is mixed to get positive electrode in 8:2 ratio；
(2) positive electrode and bonding agent mass ratio are 7:3, and positive electrode is added in a small beaker, adds second
Alcohol simultaneously ultrasonic mixing 20 minutes, bonding agent then is added by the way of being added dropwise, is sufficiently mixed bonding agent with positive electrode, obtains
To anode sizing agent；
(3) anode sizing agent is coated on collector, it is positive to get arriving in 120 DEG C of vacuum drying 12h.
The assembling of lithium-air battery:
Being assembled in the glove box full of Ar for battery carries out, and the positive electrode of just extremely above-mentioned preparation, diaphragm is glass
Fiber filter paper, electrolyte are the TEGDME solution of 0.65mol/L LiTFSI, and cathode is the metal lithium sheet of diameter 16mm.Exist first
Battery pedestal puts down lithium piece, in placing diaphragm in lithium piece, electrolyte is then added dropwise and is put into anode.The battery standing that will be assembled
8h makes electrolyte sufficiently infiltrate anode, stands 4h again after being passed through oxygen.
Comparative example 1
The preparation of lithium air battery positive electrode:
(1) anode carbon material Super P and bonding agent mass ratio are 7:3, and positive carbon materials are added in a small beaker
Material adds ethyl alcohol and ultrasonic mixing 20 minutes, and bonding agent then is added by the way of being added dropwise, and makes bonding agent and positive carbon materials
Material is sufficiently mixed, and obtains anode sizing agent；
(3) anode sizing agent is coated on collector, it is positive to get arriving in 120 DEG C of vacuum drying 12h.
The assembling of lithium-air battery:
Being assembled in the glove box full of Ar for battery carries out, and the positive electrode of just extremely above-mentioned preparation, diaphragm is glass
Fiber filter paper, electrolyte are the TEGDME solution of 0.65mol/L LiTFSI, and cathode is the metal lithium sheet of diameter 16mm.Exist first
Battery pedestal puts down lithium piece, in placing diaphragm in lithium piece, electrolyte is then added dropwise and is put into anode.The battery standing that will be assembled
8h makes electrolyte sufficiently infiltrate anode, stands 4h again after being passed through oxygen.
Comparative example 2
The preparation of lithium air battery positive electrode:
(1) anode carbon material Super P and MnO2Material is mixed to get positive electrode in 8:2 ratio；
(2) positive electrode and bonding agent mass ratio are 7:3, and positive electrode is added in a small beaker, adds second
Alcohol simultaneously ultrasonic mixing 20 minutes, bonding agent then is added by the way of being added dropwise, is sufficiently mixed bonding agent with positive electrode, obtains
To anode sizing agent；
(3) anode sizing agent is coated on collector, it is positive to get arriving in 120 DEG C of vacuum drying 12h.
The assembling of lithium-air battery:
Being assembled in the glove box full of Ar for battery carries out, and the positive electrode of just extremely above-mentioned preparation, diaphragm is glass
Fiber filter paper, electrolyte are the TEGDME solution of 0.65mol/L LiTFSI, and cathode is the metal lithium sheet of diameter 16mm.Exist first
Battery pedestal puts down lithium piece, in placing diaphragm in lithium piece, electrolyte is then added dropwise and is put into anode.The battery standing that will be assembled
8h makes electrolyte sufficiently infiltrate anode, stands 4h again after being passed through oxygen.
Comparative analysis:
(1) X-ray diffraction (XRD) map of the lithium air battery positive electrode prepared in embodiment 3 and comparative example 1 is carried out
Comparative analysis, as shown in Figure 1, it is seen that occur MoO respectively at 2 θ values is 36.5 °, 38.1 °, 41.3 ° and 53.8 °2(100)、
MoO2(002)、MoO2(101) and MoO2(102) diffraction maximum illustrates anode catalytic agent material MoO2It is sufficiently adhering to lithium air
On anode.
Lithium air battery positive electrode obtained in embodiment 3 is scanned electron microscope analysis, as shown in Figure 2, it is seen that after mixing
Positive electrode be attached in entire nickel foam network, not destroy nickel foam skeleton so that the passability of oxygen is more preferable, instead
It should more completely.
Assembled battery in embodiment 3 and comparative example 1 is subjected to electrochemical property test respectively, in current density
0.1mA·cm-2, simulated atmosphere atmosphere (21%O2+ 79%N2) under carry out discharge test.As shown in figure 3, for two groups of lithium air electricity
Pond discharge curve comparison diagram for the first time.It can be seen from the figure that the exoelectrical reaction platform in embodiment 3 appears in 2.54V, puts for the first time
Capacitance reaches 1722.2mAh/g, and the electric discharge for the first time with 2.43V exoelectrical reaction platform and 476.3mAh/g in comparative example 1 is held
Amount is compared, and chemical property is greatly improved, and illustrates the MoO with rutile structure2Do anode catalytic agent material energy
Enough increase the discharge capacity of battery, improve discharge voltage plateau, there is significant catalytic effect, can be applied to lithium-air battery.
(2) X-ray diffraction (XRD) map of the lithium air battery positive electrode prepared in embodiment 4 and comparative example 1 is carried out
Comparative analysis, as shown in Figure 4, it is seen that occur Mo respectively at 2 θ values is 35.6 °, 35.8 ° and 36.4 °17O47(061)、
Mo17O47(161) and Mo17O47(631) diffraction maximum illustrates anode catalytic agent material Mo17O47It is sufficiently adhering to lithium-air battery
On anode.
Lithium air battery positive electrode obtained in embodiment 4 is scanned electron microscope analysis, as shown in Figure 5, it is seen that after mixing
Positive electrode be attached in entire nickel foam network, not destroy nickel foam skeleton so that the passability of oxygen is more preferable, instead
It should more completely.
Assembled battery in embodiment 4 and comparative example 1 is subjected to electrochemical property test respectively, in current density
0.1mA·cm-2, simulated atmosphere atmosphere (21%O2+ 79%N2) under carry out discharge test.As shown in fig. 6, for two groups of lithium air electricity
Pond discharge curve comparison diagram for the first time.It can be seen from the figure that the exoelectrical reaction platform in embodiment 4 appears in 2.59V, puts for the first time
Capacitance reaches 1852.0mAh/g, and the electric discharge for the first time with 2.43V exoelectrical reaction platform and 476.3mAh/g in comparative example 1 is held
Amount is compared, and chemical property is greatly improved, and illustrates the Mo with rutile structure17O47Do anode catalytic agent material
It is capable of increasing the discharge capacity of battery, improves discharge voltage plateau, there is significant catalytic effect, can be applied to lithium air electricity
Pond.
(3) assembled battery in embodiment 5 and comparative example 1 is subjected to electrochemical property test respectively, in current density
0.1mA·cm-2, simulated atmosphere atmosphere (21%O2+ 79%N2) under carry out discharge test.As shown in fig. 7, for two groups of lithium air electricity
Pond discharge curve comparison diagram for the first time.It can be seen from the figure that the exoelectrical reaction platform in embodiment 5 appears in 2.58V, puts for the first time
Capacitance reaches 1837.6mAh/g, and the electric discharge for the first time with 2.43V exoelectrical reaction platform and 476.3mAh/g in comparative example 1 is held
Amount is compared, and chemical property is greatly improved, and illustrates the MoO with rutile structure2/Mo17O471:1 mixture do
Anode catalytic agent material is capable of increasing the discharge capacity of battery, improves discharge voltage plateau, has significant catalytic effect, can answer
For lithium-air battery.
(4) assembled battery in embodiment 6 and comparative example 1 is subjected to electrochemical property test respectively, in current density
0.1mA·cm-2, simulated atmosphere atmosphere (21%O2+ 79%N2) under carry out discharge test.As shown in figure 8, for two groups of lithium air electricity
Pond discharge curve comparison diagram for the first time.It can be seen from the figure that the exoelectrical reaction platform in embodiment 6 appears in 2.55V, puts for the first time
Capacitance reaches 1826.5mAh/g, and the electric discharge for the first time with 2.43V exoelectrical reaction platform and 476.3mAh/g in comparative example 1 is held
Amount is compared, and chemical property is greatly improved, and illustrates the MoO with rutile structure2/Mo17O471:2 mixture do
Anode catalytic agent material is capable of increasing the discharge capacity of battery, improves discharge voltage plateau, has significant catalytic effect, can answer
For lithium-air battery.
(5) assembled battery in embodiment 7 and comparative example 1 is subjected to electrochemical property test respectively, in current density
0.1mA·cm-2, simulated atmosphere atmosphere (21%O2+ 79%N2) under carry out discharge test.As shown in figure 9, for two groups of lithium air electricity
Pond discharge curve comparison diagram for the first time.It can be seen from the figure that the exoelectrical reaction platform in embodiment 7 appears in 2.59V, puts for the first time
Capacitance reaches 1969.0mAh/g, and the electric discharge for the first time with 2.43V exoelectrical reaction platform and 476.3mAh/g in comparative example 1 is held
Amount is compared, and chemical property is greatly improved, and illustrates the MoO with rutile structure2/Mo17O471:3 mixture do
Anode catalytic agent material is capable of increasing the discharge capacity of battery, improves discharge voltage plateau, has significant catalytic effect, can answer
For lithium-air battery.
(6) assembled battery in embodiment 3, embodiment 4 and comparative example 1, comparative example 2 is subjected to chemical property respectively
Test, in current density 0.1mAcm-2, simulated atmosphere atmosphere (21%O2+ 79%N2) under carry out discharge test.Such as Figure 10 institute
Show, is four groups of lithium-air batteries discharge curve comparison diagram for the first time.It can be seen from the figure that the electric discharge for the first time in two groups of embodiments is held
The discharge capacity value being higher than in two groups of comparative examples is measured, the Mo with rutile structure is further explainedxOyDo anode catalytic
Agent material is capable of increasing the discharge capacity of battery, improves discharge voltage plateau, has significant catalytic effect, can be applied to lithium sky
Pneumoelectric pond.
In conclusion the Mo provided by the present invention with rutile structurexOyMaterial does anode catalyst, specific surface
Product is big, and conductive effect is good, and catalytic effect is significant, increases the amplification capacity of battery, improves discharge voltage plateau；It applies simultaneously
In the lithium air battery positive electrode of the anode catalyst, mixed positive electrode is attached in entire nickel foam network, is not destroyed
The skeleton of nickel foam, so that oxygen passability is more preferable, reaction is more complete；Using in the lithium-air battery of the anode catalyst,
The insertion abjection diffusion admittance of lithium ion and electronics is more, apart from short, speed is fast, effectively improves the electrochemistry of lithium-air battery
Performance.
The present invention is further described by specific embodiment above, it should be understood that, here specifically
Description, should not be construed as the restriction for the essence of the present invention with range, and one of ordinary skilled in the art is reading this explanation
The various modifications made after book to above-described embodiment belong to the range that the present invention is protected.
Claims (9)
1. a kind of lithium air battery positive electrode catalyst material, which is characterized in that the anode catalytic agent material is MoxOyMaterial, institute
State MoxOyMaterial has rutile structure, the MoxOyMaterial is MoO2And Mo17O47Mixture；The MoO2And Mo17O47's
MoO in mixture2And Mo17O47Mass ratio be 1:1-1:3.
2. lithium air battery positive electrode catalyst material according to claim 1, which is characterized in that MoO2Powder passes through reduction
Method preparation, preparation method are as follows:
(1) silester and hydrophilic fumed silica are mixed in a certain ratio, are poured into the mixed solution of second alcohol and water, stand 20-
For 24 hours, 3-5h is calcined at 600-700 DEG C, obtains self-control SiO2Template；
(2) by a certain amount of (NH4)6Mo7O24It is dissolved in deionized water, self-control SiO is added in whipping process2Template, under 60~70
DEG C heating removal deionized water, obtain white powder；
(3) by the white powder in step (2) in 600-700 DEG C of temperature, H26-7h is calcined under reducing atmosphere；
(4) it will be taken out in step (3) through the calcined powder of reducing atmosphere, 1.8-2.4M HF be added and removes self-control SiO2Mould
Plate obtains MoO2Powder.
3. lithium air battery positive electrode catalyst material according to claim 2, which is characterized in that silicic acid second in step (1)
The mixing ratio of ester and hydrophilic fumed silica is 5:5 or 7:3；The mixing ratio of second alcohol and water is 6:4 or 8:2.
4. lithium air battery positive electrode catalyst material according to claim 1, which is characterized in that Mo17O47Passing through of powder
Learn vapour deposition process preparation, preparation method are as follows:
(1) a certain amount of Mo powder is added in CVD device, keeping central temperature is 760-780 DEG C；
(2) when oxygen pressure is 1.1-1.2Torr, with 0.05-0.06m3The speed of/h is passed through oxygen, reacts 30-35min, obtains
To Mo17O47Powder.
5. a kind of lithium air battery positive electrode, which is characterized in that including the described in any item lithium air battery positive electrodes of claim 1-4
Catalyst material.
6. a kind of preparation method of lithium air battery positive electrode described in claim 5, which is characterized in that it is prepared using cladding process,
Include the following steps:
(1) by positive carbon material and MoxOyMaterial is mixed to get positive electrode in 5:5 or 7:3 or 8:2 ratio；
(2) by positive electrode and bonding agent by uniformly mixed after mass ratio ultrasound 20-30 minutes of 7:3 or 8:2；
(3) on a current collector by the good mixture coating of ultrasound in step (2), it is obtained after dry 10-12h at 100-120 DEG C
Lithium air battery positive electrode.
7. the preparation method of lithium air battery positive electrode according to claim 6, which is characterized in that used in step (1)
Carbon material is one of Super P, carbon nanotube, graphene.
8. the preparation method of lithium air battery positive electrode according to claim 6, which is characterized in that the bonding in step (2)
Agent is one of PVDF, LA132, SBR+CMC, polyvinyl alcohol.
9. the preparation method of lithium air battery positive electrode according to claim 6, which is characterized in that the afflux in step (3)
Body is copper mesh or nickel foam, and the diameter of the collector is 12-16mm.
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| CN105870466A (en) * | 2016-04-20 | 2016-08-17 | 四川大学 | Lithium-air battery positive electrode employing hydroxyl cobalt oxide as catalyst and preparation method of positive electrode |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105870466A (en) * | 2016-04-20 | 2016-08-17 | 四川大学 | Lithium-air battery positive electrode employing hydroxyl cobalt oxide as catalyst and preparation method of positive electrode |
Non-Patent Citations (3)
| Title |
|---|
| "An overview of metal oxide materials as electrocatalysts and supports for polymer electrolyte fuel cells";Zhonghua Zhang，et al.;《Energy Environ. Sci.》;20140428;第7卷(第8期);第2535-2558页 * |
| "Bioinspired Synthesis of Hierarchically Porous MoO2/Mo2C Nanocrystal Decorated N‑Doped Carbon Foam for Lithium−Oxygen Batteries";Yan Lu，et al.;《Chem. Mater.》;20160728;第5743-5752页 * |
| "Porous metallic MoO2-supported MoS2 nanosheets for enhanced electrocatalytic activity in the hydrogen evolution reaction";Linjing Yang，et al.;《Nanoscale》;20150210;第7卷(第12期);第5203-5208页 * |
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