CN109904464A - Lithium-air battery three-dimensional self-supporting positive electrode and its preparation method and application - Google Patents
Lithium-air battery three-dimensional self-supporting positive electrode and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to lithium-air battery three-dimensional self-supporting positive electrodes and its preparation method and application, the positive electrode is the compound of carbon coating transition metal phosphide nanoparticle and the compound composition of three-dimensional self-supporting carbon material, and the gross mass that the carbon coating transition metal phosphide nanoparticle accounts for compound is 10-50wt%.The invention has the advantages that 1) present invention utilizes discarded, cheap biomass for raw material, the use using carriers such as carbon paper, carbon cloth, nickel foam, grapheme foam or electrospun fiber membranes is avoided, battery production cost can be greatly reduced；(2) present invention process is simple, convieniently synthesized, easily realization scale application etc..
Description
Technical field
The invention belongs to inorganic nano material and new energy materials fields, are related to rechargeable lithium secondary battery, are related to one kind
Lithium-air battery three-dimensional self-supporting positive electrode and its preparation method and application.
Background technique
Increasingly serious due to environmental pollution and energy crisis, the development and utilization of green novel energy source is current research heat
Point.Lithium-air battery is using lithium metal as cathode, and porous electrode is anode, a kind of cell body of oxygen as a positive electrode active material
System.In discharge process, oxygen by the external world enter battery, under the action of catalyst with from cathode through external circuit flow through come electronics and
The Li transmitted through electrolyte+Electrode reaction occurs, generates with lithium peroxide (Li2O2) based on product, and release energy.
Theoretically, oxygen is unrestricted as anode reactant, and the capacity of battery is only dependent upon lithium electrode, and theoretical specific energy is up to
11680Wh/kg, close to conventional fossil fuel energy density (13000Wh/kg or so) therefore, lithium-air battery is considered
It is one of most commercial prospects new energy technology (Zhao Z.et al., Angewandte Chemie-
International Edition, 2018,57,3874-3886).
However, organic electrolyte system lithium-air battery from practical application there are also larger gap, 1. positive electrode catalytic efficiency
Lower, in charge and discharge process, there are biggish overpotentials, may cause the decomposition of electrolyte and binder, cause cell performance
It can decay rapidly；2. discharging product does not dissolve in electrolyte, it can be deposited on the duct of air electrode, cause gas delivery passage stifled
Plug, electrode polarization and impedance increase, and cause battery premature failure.In order to solve these problems, develop and design novel anode
Material has profound significance to the development of lithium-air battery.
Lithium-air battery with traditional three-dimensional self-supporting positive electrode be usually use carbon paper, nickel foam, grapheme foam,
Electrospun fiber membrane etc. is carrier, surface growth catalyst.However, these material costs are higher, and synthesis process is complicated, is unfavorable for
The commercialization of lithium-air battery.In addition, the materials itself such as carbon paper and nickel foam are precipitated hydrogen reduction and oxygen and do not have catalysis energy
Power, therefore in the case where calculating entire cathode quality, true lithium-air battery specific capacity is not high.Luo et al. is using wood
Head is prepared for a kind of three-dimensional self-supporting electrode of N doping by high-temperature calcination, ammonia activation for raw material, but battery performance is still
Unsatisfactory (Luo J.et al., Nano Research, 2017,10,4318-4326).Song et al. on this basis,
By introduce Ru catalyst, charging overpotential is greatly reduced, and improve battery cycle life (Song H.et al.,
Advanced Energy Materials, 2018,8,1701203).However, the reserves of noble metal Ru are limited, it is expensive, no
Suitable for large-scale application in lithium-air battery.
In conclusion urgent need is developed, a kind of raw material sources are extensive, and simple process and low cost is suitable for large-scale production
Anode material for lithium-air battery and its preparation process.
Summary of the invention
Above-mentioned lithium-air battery there are aiming at the problem that, the purpose of the present invention is to provide a kind of high performance lithium air electricity
Pond positive electrode and preparation method thereof；The present invention also aims to the three-dimensional structures using biomass, obtain three-dimensional self-supporting
Positive electrode, side reaction caused by avoiding in positive electrode due to using binder occurs；The present invention also aims to benefits
With biomass porous structure and biggish specific surface area, efficient electrolyte and oxygen transmission channel are provided, and is produced for electric discharge
Object provides sufficiently large storage space, improves the capacity of lithium-air battery；The present invention also aims to can be in biological material
The surface deposited metal organic framework material of material prepares the carbon-clad metal phosphide nanoparticle of the core-shell structure of high activity,
Enhance electrocatalytic oxidation reduction and oxygen precipitation ability, reduces charge and discharge overpotential, improve the cyclical stability of lithium-air battery.
The present invention provides a kind of lithium-air battery three-dimensional self-supporting positive electrode and its preparation method and application, of the invention
Technical solution is:
Lithium-air battery three-dimensional self-supporting positive electrode, the positive electrode are carbon coating transition metal phosphide nanoparticle
With the compound of the three-dimensional compound composition of self-supporting carbon material, the carbon coating transition metal phosphide nanoparticle accounts for compound
Gross mass is 10-50wt%.
A method of preparing lithium-air battery three-dimensional self-supporting positive electrode, comprising the following steps:
(1) it using biomass as raw material, is placed in the solution of metal salt and additive, is slow added into containing organic linking
The solution of agent reacts 1-24h under 20-180 degree, obtain the biomass of carried metal organic framework material, will obtain later
Product cleaning removes the metal-organic framework materials of surface growth loosely, obtains biomass presoma after dry；
(2) the biomass presoma of preparation is placed in tube furnace, under inert atmosphere, with 0.5-10 degree/min heating
Rate is warming up under 250-1000 degree, keeps the temperature 1-12h, is obtained three-dimensional self-supporting and is adulterated carbon material supported carbon coating transition gold
Belong to nanoparticle；
(3) three-dimensional self-supporting is adulterated into carbon material supported carbon coating transition metal nanoparticles and mixes phosphorus source, be placed in pipe
It in formula furnace, under inert atmosphere, with 0.5-10 degree/min heating rate, is warming up under 250-1000 degree, keeps the temperature 1-12h, obtain
Carbon material supported carbon-clad metal phosphide nanoparticle is adulterated to three-dimensional self-supporting；Wherein, phosphorus source is red phosphorus or Asia
One of sodium hypophosphite, the three-dimensional self-supporting adulterate carbon material supported carbon coating transition metal nanoparticles and phosphorus source
Mass ratio is 1:1~20.
In the step of described (1), biomass is the biomass with three-dimensional porous structure, is cut into diameter after cleaning up
For 10-20mm, with a thickness of the disk of 0.5-10mm, the 60-100 degree drying for standby in baking oven.
The pore diameter range of the biomass is 1nm~100um；The density of the biomass is 0.1~200mg/cm3, institute
State 0.1~10cm of Kong Rongwei of biomass3/g。
The metal salt is acetate, nitrate, sulfate, oxalates or the chlorine of zinc, cobalt, nickel, iron, copper, zirconium and titanium
One or more of compound cooperates according to arbitrary proportion.
Solvent used in the metal salt solution and organic linking agent be deionized water, ethyl alcohol, methanol, ethylene glycol, N,
Dinethylformamide, dimethyl acetamide, dimethyl sulfoxide or N, in N- diethylformamide any one or according to appointing
Meaning ratio cooperates several.
The additive is trisodium citrate, citric acid, polyvinyl alcohol, Pidolidone, phthalic acid, succinic acid, acetic acid
In any one or a few cooperate according to arbitrary proportion.
The organic linking agent be the potassium ferricyanide, potassium cobalticyanide, nickel potassium cyanide, 2-methylimidazole, 1,3,5- benzenetricarboxylic acid,
Triethylamine, 1,4- rutgers, 4,4', 4 "-(three base of 1,3,5- triazine -2,4,6-) three-benzoic acid, 2- amino are to benzene
Any one or a few in dioctyl phthalate, terephthalic acid (TPA) cooperates according to arbitrary proportion.
The molar ratio of the metal salt, additive and organic linking agent is 1:0.01~0.5:0.1~10.
A kind of positive electrode, is used to prepare lithium air battery positive electrode.
The invention has the advantages that (1) present invention is raw material using discarded, cheap biomass, avoid using carbon paper, carbon
The use of the carriers such as cloth, nickel foam, grapheme foam or electrospun fiber membrane can greatly reduce battery production cost；(2) this hair
Bright simple process, it is convieniently synthesized, easily realize scale application；(3) the three-dimensional self-supporting carbon of present invention preparation biomass derived
Material, acts not only as the carrier of catalyst, and hetero atom abundant in body phase can also form active site, with carbon
Clad metal nano particle forms synergistic effect effect, improves battery performance；
(4) present invention uses metal-organic framework materials for catalyst precursor, and metal phosphide not only may be implemented and urge
Agent it is evenly dispersed, and be formed by core-shell structure, the carbon of outer layer is also beneficial to protection metal phosphide nanoparticle
Reunite, realizes the extension of battery cycle life.
Specific embodiment
Embodiment 1: lithium-air battery three-dimensional self-supporting positive electrode, the positive electrode are carbon coating transition metal phosphide
The compound of nanoparticle and the compound composition of three-dimensional self-supporting carbon material, specifically the preparation method is as follows: pomelo peel is peelled off outer layer
Clean with deionized water, washes of absolute alcohol after yellow crust, being cut into diameter is 16mm, the disk with a thickness of 2mm, in baking oven
In 60 degree of lower drying for standby.
0.87g Nickelous nitrate hexahydrate is taken, 1.325g trisodium citrate is dissolved in 20ml deionized water, and it is clean that 100mg is added
Net pomelo peel, stirs 6h, and ultrasonic 30min is made into solution A；
The 0.6585g potassium ferricyanide is taken, is dissolved in 20ml deionized water, is made into B solution；
In the case of stirring, B solution is slowly added to solution A, after persistently stirring 15min, is placed in aging at room temperature
24h；
There is the pomelo peel of the Prussian blue similar object (one kind of metal-organic framework materials) of NiFe to take out final growth, uses
It is deionized water, washes of absolute alcohol each 3 times, dry that biomass presoma is spare under 60 degree in baking oven；The metal is organic
Framework material is mainly grown in the surface or body phase for being deposited on biomass, the metal-organic framework materials can also be ZIF,
BTC,UiO,HKUST.Above-mentioned biomass presoma is mixed and is placed in tube furnace, under an ar atmosphere, is warming up to 2 degree/min
1000 degree, 2h is kept the temperature, obtained three-dimensional self-supporting is calcined and adulterates carbon material supported carbon coating NiFe nanoparticle.
Above-mentioned prepared three-dimensional self-supporting is adulterated into carbon material supported carbon coating NiFe nanoparticle and red phosphorus by 1:1
Mixing, is placed in tube furnace, under an ar atmosphere, is warming up to 700 degree with 2 degree/min, keeps the temperature 6h, calcines obtained three-dimensional self-supporting and mixes
Miscellaneous carbon material supported carbon coating NiFeP nanoparticle, and it is directly used as the anode of lithium-air battery.
Embodiment 2: lithium-air battery three-dimensional self-supporting positive electrode, the positive electrode are carbon coating transition metal phosphide
The compound of nanoparticle and the three-dimensional compound composition of self-supporting carbon material, it is specific the preparation method is as follows:
Clean with deionized water, washes of absolute alcohol after watermelon peel is peelled off outer layer shagreen, being cut into diameter is 16mm, thickness
Degree is the disk of 2mm, 60 degree of lower drying for standby in baking oven.
0.87g cabaltous nitrate hexahydrate is taken, 1.325g trisodium citrate is dissolved in 20ml deionized water, and it is clean that 100mg is added
Net watermelon peel, stirs 6h, and ultrasonic 30min is made into solution A；
0.665g potassium cobalticyanide is taken, is dissolved in 20ml deionized water, is made into B solution；
In the case of stirring, B solution is slowly added to solution A, after persistently stirring 15min, is placed in aging at room temperature
24h；
There is the watermelon peel of the Prussian blue similar object of Co to take out final growth, with deionized water, washes of absolute alcohol each 3
Secondary, it is spare to form biomass presoma for 60 degree of lower dryings in baking oven；
Above-mentioned biomass presoma is placed in tube furnace, under an ar atmosphere, is warming up to 900 degree with 2 degree/min, heat preservation
2h calcines obtained three-dimensional self-supporting and adulterates carbon material supported carbon coating Co nanoparticle；
Above-mentioned prepared three-dimensional self-supporting is adulterated into carbon material supported carbon coating Co nanoparticle and red phosphorus by 1:10
Mixing, is placed in tube furnace, under an ar atmosphere, is warming up to 800 degree with 5 degree/min, keeps the temperature 3h, calcines obtained three-dimensional self-supporting and mixes
Miscellaneous carbon material supported carbon coating CoP nanoparticle, and it is directly used as the anode of lithium-air battery.
Embodiment 3: lithium-air battery three-dimensional self-supporting positive electrode, the positive electrode are carbon coating transition metal phosphide
The compound of nanoparticle and the three-dimensional compound composition of self-supporting carbon material, it is specific the preparation method is as follows:
Silk cocoon deionized water, washes of absolute alcohol is clean, and being cut into diameter is 16mm, the disk with a thickness of 2mm, in baking
60 degree of lower drying for standby in case.
0.87g cabaltous nitrate hexahydrate is taken, is dissolved in 30ml anhydrous methanol, the silk cocoon of 100mg cleaning is added, stirs 6h,
Ultrasonic 30min, is made into solution A；
1.476g methylimidazole is taken, is dissolved in 30ml anhydrous methanol, is made into B solution；
In the case of stirring, B solution is slowly added to solution A, after persistently stirring 30min, is placed in aging at room temperature
24h；
There is the silk cocoon of ZIF to take out final growth, each 3 times with washes of absolute alcohol, is dried to obtain under 60 degree in baking oven
Biomass presoma is spare；
Above-mentioned biomass presoma is placed in tube furnace, under an ar atmosphere, is warming up to 900 degree with 2 degree/min, heat preservation
2h calcines obtained three-dimensional self-supporting and adulterates carbon material supported carbon coating Co nanoparticle.
Above-mentioned prepared three-dimensional self-supporting is adulterated to carbon material supported carbon coating Co nanoparticle and sodium hypophosphite
It mixes, is placed in tube furnace by 1:10, under an ar atmosphere, be warming up to 300 degree with 2 degree/min, keep the temperature 2h, calcine and three-dimensional is made certainly
Carbon material supported carbon coating CoP nanoparticle is adulterated in support, is then cleaned by ultrasonic using deionized water, is directly used as after dry
The anode of lithium-air battery.
Embodiment 4: lithium-air battery three-dimensional self-supporting positive electrode, the positive electrode are carbon coating transition metal phosphide
The compound of nanoparticle and the compound composition of three-dimensional self-supporting carbon material, specifically the preparation method is as follows: pomelo peel is peelled off outer layer
Clean with deionized water, washes of absolute alcohol after yellow crust, being cut into diameter is 16mm, the disk with a thickness of 2mm, in baking oven
In 60 degree of lower drying for standby.
0.2g copper acetate is taken, 0.073g Pidolidone is dissolved in 40ml deionized water, and the shaddock of 100mg cleaning is added
Skin, stirs 6h, and ultrasonic 30min is made into solution A；
1,3,5- benzenetricarboxylic acid of 0.14g is taken, is dissolved in 40ml dehydrated alcohol, is made into B solution；
In the case of stirring, B solution is slowly added to solution A, after persistently stirring 30min, is placed in aging at room temperature
24h；
There is the pomelo peel of Cu-BTC to take out final growth, with deionized water, washes of absolute alcohol each 3 times, in baking oven
It is spare that biomass presoma is dried to obtain under 60 degree；
Above-mentioned biomass presoma is placed in tube furnace, under an ar atmosphere, is warming up to 900 degree with 2 degree/min, heat preservation
2h calcines obtained three-dimensional self-supporting and adulterates carbon material supported carbon coating Cu nanoparticle.
Above-mentioned prepared three-dimensional self-supporting is adulterated to carbon material supported carbon coating Cu nanoparticle and sodium hypophosphite
It mixes, is placed in tube furnace by 1:20, in N2Under atmosphere, 250 degree are warming up to 1 degree/min, keeps the temperature 3h, calcined and three-dimensional is made certainly
Carbon material supported carbon coating CuP nanoparticle is adulterated in support, is then cleaned by ultrasonic using deionized water, is directly used as after dry
The anode of lithium-air battery.
The synthesis of the Prussian blue similar object powder of comparative example 1:Ni-Fe: it is identical as the synthesis condition of embodiment 1, only
It is to be added without pomelo peel.
Above-mentioned powder is placed in tube furnace, under an ar atmosphere, is warming up to 1000 degree with 2 degree/min, keeps the temperature 2h, calcining system
Obtain the carbon coating NiFe nanoparticle of final core-shell structure.
The carbon coating NiFe nanoparticle of above-mentioned prepared core-shell structure is mixed with red phosphorus by 1:1, tube furnace is placed in
In, under an ar atmosphere, 700 degree are warming up to 2 degree/min, keeps the temperature 6h, calcines the carbon coating NiFeP nanoparticle that core-shell structure is made
Son.
Carbon paper is in deionized water, acetone, dehydrated alcohol, each ultrasound 30min, removes the pollutant and oil of surface attachment
Stain, 60 degree of lower drying for standby in baking oven.
Take the carbon coating NiFeP nanoparticle of the core-shell structure of above-mentioned preparation, (mass ratio is the Nafion solution of 5wt%
9:1), it is made into slurry, is sprayed on carbon paper surface, 80 degree of drying for standby in baking oven, wherein carbon coating NiFe nanoparticle is in carbon
Loading control on paper is 1 ± 0.1mg/cm2。
Above-mentioned the electrode obtained is cut into the disk that diameter is 12mm, the anode as lithium-air battery.
Comparative example 2: it is clean with deionized water, washes of absolute alcohol after pomelo peel is peelled off outer layer yellow crust, it cuts
It is 16mm, with a thickness of the disk of 2mm at diameter, 60 degree of lower drying for standby in baking oven.
The pomelo peel of above-mentioned cleaning is mixed with red phosphorus by 1:1, is placed in tube furnace, under an ar atmosphere, with 2 degree/min liter
Temperature keeps the temperature 6h to 700 degree, and parkerized pomelo peel is made in calcining.
It is placed in above-mentioned in tube furnace by parkerized pomelo peel, under an ar atmosphere, is warming up to 1000 with 2 degree/min
Degree keeps the temperature 2h, calcines and final product is made, and be directly used as the anode of lithium-air battery.
By anode obtained by embodiment 1,2,3,4 and comparative example 1,2, group in the glove box of argon atmosphere is put into after weighing
Button lithium-air battery is filled, lithium piece makees cathode, and Whatman glass fibre is diaphragm, the bis trifluoromethyl sulfimide lithium of 1.0M
(LiTFSI) solution in tetraethyleneglycol dimethyl ether (TEGDME) solvent is dissolved in as electrolyte, is assembled into glove box
CR2025 button cell.The battery assembled is placed in glove box and carries out electrochemical property test afterwards for 24 hours, test temperature is
Room temperature, test voltage range are 2.0~4.5V.The calculating of specific capacity of the present invention is calculated by the basis of positive gross mass
Specific capacity, electric current calculates with electrode area.
Experimental effect analysis: in 0.1mA/cm2Current density under, to lithium-air battery carry out charge-discharge test.Using
Its first discharge specific capacity of the electrode material of the preparation of embodiment 1 is up to 1450mAh/g, and coulombic efficiency is up to 99%.Limiting electricity
Pressure is 2-4.5V, capacity cutoff 0.3mAh/cm2, current density 0.1mA/cm2In the case where carry out loop test, using reality
The electrode material for applying the preparation of example 1 can stablize circulation 290 times.However, using the lithium-air battery of comparative example 1 and 2, in phase
With under the conditions of, first discharge specific capacity is only 141 and 98mAh/g respectively；Coulombic efficiency is only 56% and 54% respectively；It follows
The ring service life is only 3 times and 2 times respectively.
The discussion and description of front are the citings of the specific embodiment of the invention, but they do not mean that the limit operated by this
System.According to the present invention, many improvements and changes are apparent to those skilled in the art.Biological material source is rich
Richness, all biological materials with three-dimensional porous structure, belongs to the protection category of the invention；In addition, metal organic framework material
Expect it is many kinds of, it is most of to can apply to this scheme, also belong to the protection category of the invention.Claim includes all etc.
Effect description, defines the scope of the present invention.
Claims (10)
1. lithium-air battery three-dimensional self-supporting positive electrode, which is characterized in that the positive electrode is carbon coating transition metal phosphatization
The compound of object nanoparticle and the compound composition of three-dimensional self-supporting carbon material, the carbon coating transition metal phosphide nanoparticle
The gross mass for accounting for compound is 10-50wt%.
2. a kind of method for preparing lithium-air battery three-dimensional self-supporting positive electrode described in claim 1, which is characterized in that packet
Include following steps:
(1) it using biomass as raw material, is placed in the solution of metal salt and additive, is slow added into containing organic bridging agent
Solution reacts 1-24h under 20-180 degree, obtains the biomass of carried metal organic framework material, the product that will be obtained later
Cleaning removes the metal-organic framework materials of surface growth loosely, obtains biomass presoma after dry；
(2) the biomass presoma of preparation is placed in tube furnace, under inert atmosphere, with 0.5-10 degree/min heating speed
Rate is warming up under 250-1000 degree, is kept the temperature 1-12h, is obtained three-dimensional self-supporting and adulterate carbon material supported carbon coating transition metal
Nanoparticle；
(3) three-dimensional self-supporting is adulterated into carbon material supported carbon coating transition metal nanoparticles and mixes phosphorus source, be placed in tube furnace
In, it under inert atmosphere, with 0.5-10 degree/min heating rate, is warming up under 250-1000 degree, keeps the temperature 1-12h, obtain three
Dimension self-supporting adulterates carbon material supported carbon-clad metal phosphide nanoparticle；Wherein, phosphorus source is red phosphorus or sub- phosphorus
One of sour sodium, the three-dimensional self-supporting adulterate the quality of carbon material supported carbon coating transition metal nanoparticles and phosphorus source
Ratio is 1:1~20.
3. according to the method described in claim 2, it is characterized in that, it is described the step of (1) in, biomass is more with three-dimensional
The biomass of pore structure, it is 10-20mm, the disk with a thickness of 0.5-10mm, the 60- in baking oven that diameter is cut into after cleaning up
100 degree of drying for standby.
4. according to the method in claim 2 or 3, which is characterized in that the pore diameter range of the biomass is 1nm~100um；
The density of the biomass is 0.1~200mg/cm3, 0.1~10cm of Kong Rongwei of the biomass3/g。
5. according to the method described in claim 2, it is characterized in that, the metal salt is zinc, cobalt, nickel, iron, copper, zirconium and titanium
One or more of acetate, nitrate, sulfate, oxalates or chloride cooperate according to arbitrary proportion.
6. according to the method described in claim 2, it is characterized in that, molten used in the metal salt solution and organic linking agent
Agent is deionized water, ethyl alcohol, methanol, ethylene glycol, N,N-dimethylformamide, dimethyl acetamide, dimethyl sulfoxide or N, N-
In diethylformamide any one or according to arbitrary proportion cooperation it is several.
7. according to the method described in claim 2, it is characterized in that, the additive is trisodium citrate, citric acid, polyethylene
Alcohol, Pidolidone, phthalic acid, succinic acid, any one or a few in acetic acid cooperate according to arbitrary proportion.
8. according to the method described in claim 2, it is characterized in that, the organic linking agent is the potassium ferricyanide, potassium cobalticyanide, cyanogen
Change nickel potassium, 2-methylimidazole, 1,3,5- benzenetricarboxylic acid, triethylamine, 1,4- rutgers, 4,4', 4 "-(1,3,5- tri-
Three base of piperazine -2,4,6-) three-benzoic acid, 2- amino terephthalic acid (TPA), any one or a few in terephthalic acid (TPA) be according to any
Ratio cooperation.
9. according to the method described in claim 2, it is characterized in that, mole of the metal salt, additive and organic linking agent
Than for 1:0.01~0.5:0.1~10.
10. a kind of positive electrode, which is characterized in that be prepared, be used to prepare using claim 2 to 9 any one method
Lithium air battery positive electrode.
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| CN113860291A (en) * | 2021-08-25 | 2021-12-31 | 天津大学 | Method for in-situ synthesis of self-supporting three-dimensional graphene foam and composite material thereof |
| CN113851252A (en) * | 2021-09-13 | 2021-12-28 | 江西龙泰新材料股份有限公司 | Composite conductive agent, preparation method thereof and preparation method of conductive coating material |
| CN113851252B (en) * | 2021-09-13 | 2023-08-04 | 江西龙泰新材料股份有限公司 | Composite conductive agent and preparation method thereof, and preparation method of conductive coating material |
| CN113851663A (en) * | 2021-09-23 | 2021-12-28 | 广东省国研科技研究中心有限公司 | Magnesium air battery catalyst, magnesium air battery air cathode and preparation method thereof, magnesium air battery and electric equipment |
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Application publication date: 20190618 |