CN106848340B - A kind of preparation method of hypopolarization lithium-air battery anode catalytic material - Google Patents
A kind of preparation method of hypopolarization lithium-air battery anode catalytic material 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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
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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
- H01M12/08—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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Abstract
The present invention relates to a kind of preparation methods of hypopolarization lithium-air battery anode catalytic material, belong to electrochemical technology field.This method synthesis technology is simple, high production efficiency, Synchronos method introducings greatly improves noble metal in the dispersibility of carbon material surface, reduces noble metal dosage, is conducive to control cost large-scale production.And the method for the present invention is easy to operate, easy control of reaction conditions, as a result reproducible.The cost of material is low, chemical stability is good, large specific surface area for the hypopolarization lithium-air battery anode catalytic prepared using this method, and catalytic activity is high, and the battery specific capacity being assembled into is high, polarization is low, forthright good again.Compared with pure carbon material catalyst, catalytic efficiency is significant, and battery overpotential is low, specific capacity improves 8 times, is all significantly improved in terms of multiplying power and cycle performance.
Description
Technical field
The present invention relates to a kind of preparation method of hypopolarization lithium-air battery anode catalytic material, more particularly to one kind are low
Polarization, high rate capability, high stability lithium-air battery anode catalytic material preparation method, belong to electrochemical technology field.
Background technique
With the development of modern humans society, energy and environment problem is increasingly severe, has become obstruction modern science and technology
The significant obstacle that development is improved with human living standard.Existing energy system is mostly based on fossil energy, however as stone
Change petering out and using getting worse of climatic issues caused by fossil fuel for the energy.Therefore, exploitation uses efficient
Clean type new energy is allowed to that traditional fossil resource is gradually replaced to have great significance.Among all secondary cell systems,
Lithium-air battery is acknowledged at present
5-10 times of existing lithium ion battery, for lithium metal, energy density is up to 11140Wh/Kg, and its anode reaction
Object is the oxygen in air, will not emission greenhouse gas, relative to lithium ion battery, heavy metal usage amount is reduced, and is considered
It is the ideal electrochmical power source of substitute fossil fuels, while more meets the requirement of power battery.Although lithium-air battery passes through
Laboratory research in nearly 10 years has been gone through, has also achieved many great achievements, but everyway waits to solve there are many more problem
Certainly.Among these, it is exactly that anode catalyst is two-way in discharge and recharge reaction for one of maximum obstruction of lithium-air battery development to urge
Change the slow feature of dynamics.Slow dynamic process directly results in air cell, and to reset electric polarization big, cycle performance is low,
High rate performance is poor, it is long-term simultaneously it is easy to charge under high voltages make that electrolyte and conductive agent decompose, by-product increases, to influence
The service life of battery.In numerous lithium-air battery catalysis materials, noble metal catalyst (gold, platinum, ruthenium, palladium etc.) property is steady
Fixed, catalytic activity is high, can significantly reduce charge and discharge overpotential, improves battery efficiency and high rate performance.Document report makes
Charge and discharge overpotential can be made to be reduced to 1V once under conditions of precious metal catalyst.On the one hand, lesser polarization can be improved
Energy utilization rate, it is energy saving；On the other hand, reduce polarization make battery carried out under low potential charging can effectively avoid by
In high potential and caused by electrolytic decomposition to reduce the generation of by-product improve the service life of battery.However, using noble metal
The most important problem of catalyst is that it is expensive, and excessively high cost makes these catalyst can not large-scale commercial.Cause
This, design and synthesis low content of noble metal composite catalyst plays an important role for the application and development of lithium-air battery, and promotees
It realizes commercialized key factor early into it, significant role is played using new energy for reasonable high efficiency low cost.In order to drop
The good result of low guaranteed noble metal catalyst, while the use cost of catalyst is reduced, mainly there are several types of methods at present
It improves.First, exploitation precious metal alloys, are made alloy for noble metal and the lower metal of price, just according to a certain percentage
When novel alloy proportion meeting so that guaranteed price reduce while, increase catalysis selectivity and improve catalysis work
Property.Second, improving the active site of catalyst under equal conditions, it is supported on catalyst is as uniform as possible on carrier, it is maximum
Efficiency uses each atom.Third, the high noble metal nano particles for being catalyzed crystal face living of selectivity synthesis exposure.
Summary of the invention
The purpose of the present invention is to propose to a kind of preparation methods of hypopolarization lithium-air battery anode catalytic material, by same
The carbon material supported noble metal catalyst that stage reduction method obtains, noble metal and basal body interface effect are reinforced, and can significantly improve just
The chemical property (circulation volume, high rate performance etc.) of pole catalysis material, and the preparation method has simple process, product easy
In separation, feature at low cost, bullion content is reduced, and is more suitable for controlling cost large-scale production.
The preparation method of hypopolarization lithium-air battery anode catalytic material proposed by the present invention, comprising the following steps:
(1) oxidation for 15mL concentration being 5~10mg/mL graphene oxide solution or being 5~10mg/mL by 15mL concentration
Carbon nano-tube solution, which is added in 60mL deionized water, to be diluted, and ultrasonication 30 minutes, is uniformly dispersed；Add 5mL concentration
Hydrate ruthenium trichloride (the RuCl that palladium chloride aqueous solution or 5mL concentration for 0.8-2.0mg/mL are 1.0-2.5mg/mL3·
3H2O), it is ultrasonically treated 15 minutes and is uniformly dispersed, stirs 8~12 hours, be homogenized；By 5mL mass percentage concentration be 70~
85% hydrazine hydrate solution is added dropwise in the homogenate being stirred, and stirs 15 minutes, is transferred to the hydrothermal reaction kettle of polytetrafluoro liner
In, it is reacted 10~14 hours at 160 DEG C~180 DEG C, obtains reaction product；
(2) reaction product of above-mentioned steps (1) is washed with water repeatedly, filtered, until solution is in neutrality, it then will washing
The product crossed is 20~26 hours dry in vacuum freeze-drying machine, until dehydration completely, obtains desciccate；
(3) with 3 DEG C~5 DEG C/min of heating rate, it is warming up to 400~600 DEG C under the nitrogen protection of flowing, will do
Dry product is annealed 1~3 hour, is cooled to room temperature with the furnace, is obtained hypopolarization lithium-air battery anode catalytic material.
The preparation method of hypopolarization lithium-air battery anode catalytic material proposed by the present invention, its advantage is that:
The method of the present invention synthesis technology is simple, high production efficiency, and the introducing of Synchronos method greatly improves noble metal in carbon
The dispersibility of material surface, reduces noble metal dosage, reduces catalyst cost, is conducive to control cost large-scale production.And
And the method for the present invention raw material is few, easy to operate, easy control of reaction conditions, with yield, big, result repeats obtained product
The advantages that property is good.Carbon material-noble metal anode composite catalyst noble metal the content prepared using this method is low, and cost is few, changes
Learn that stability is good, large specific surface area, catalytic activity is high, and the battery specific capacity being assembled into is high, polarization is low, high rate performance due to.With
Pure carbon material catalyst is compared, and catalytic efficiency is significant, battery overpotential is low, in terms of specific capacity superelevation, multiplying power and cycle performance all
It is significantly improved.
Detailed description of the invention
Fig. 1 is that the X that graphene-supported palladium (Pd-rGO) composite material of this method preparation is compared with pure graphene (rGO) is penetrated
Ray diffraction diagram (XRD).
Fig. 2 is that graphene-supported palladium (Pd-rGO) composite catalyst of this method preparation and pure graphene (rGO) are catalyzed lithium
Polarize comparison under air cell 200mA/g current density.
Fig. 3 is that graphene-supported palladium (Pd-rGO) composite catalyst of this method preparation and pure graphene (rGO) are catalyzed lithium
Capacity cutoff recycles comparison diagram under air cell 1A/g current densities.
Fig. 4 is that graphene-supported palladium (Pd-rGO) composite catalyst of this method preparation is catalyzed lithium-air battery at different times
Specific discharge capacity comparison diagram under rate.
Specific embodiment
The preparation method of hypopolarization lithium-air battery anode catalytic material proposed by the present invention, comprising the following steps:
(1) 15mL concentration is obtained for 5~10mg/mL by Hummers method (J.Am.Chem.Soc.1958,80,1339)
Graphene oxide solution or be that the oxide/carbon nanometer tube solution that 5~10mg/mL is obtained by Hummers method is added by 15mL concentration
It dilutes, ultrasonication 30 minutes, is uniformly dispersed into 60mL deionized water；Adding 5mL concentration is 0.8-2.0mg/mL's
Palladium chloride (PdCl2) aqueous solution or 5mL concentration be 1.0-2.5mg/mL hydrate ruthenium trichloride (RuCl3·3H2O), it is ultrasonically treated
It is uniformly dispersed within 15 minutes, stirs 8~12 hours, be homogenized；The hydrazine hydrate solution for being 70~85% by 5mL mass percentage concentration
It is added dropwise in the homogenate being stirred, stirs 15 minutes, be transferred in the hydrothermal reaction kettle of polytetrafluoro liner, at 160 DEG C~180 DEG C
Lower reaction 10~14 hours, obtains reaction product；
(2) reaction product of above-mentioned steps (1) is washed with water repeatedly, filtered, until solution is in neutrality (PH test paper inspection
Survey), it is then that washed product is 20~26 hours dry in vacuum freeze-drying machine, until dehydration completely, obtains desciccate；
(3) with 3 DEG C~5 DEG C/min of heating rate, it is warming up to 400~600 DEG C under the nitrogen protection of flowing, will do
Dry product is annealed 1~3 hour, is cooled to room temperature with the furnace, is obtained the lithium-air battery anode catalyst of hypopolarization.
The embodiment of the method for the present invention is described below:
Embodiment one:
(1) 15mL 5mg/mL is added to dilute in 60mL deionized water by the graphene oxide solution that Hummers method obtains
It releases, ultrasonic 30min is uniformly dispersed.Add the PdCl of 5mL 1.5mg/mL2Aqueous solution.Ultrasonic 15min is uniformly dispersed, stirring 8
~12 hours.The hydrazine hydrate solution of 5mL 70~85% is added dropwise in the homogenate that will be stirred, and stirs 15min, is transferred to poly- four
In the hydrothermal reaction kettle of fluorine liner.160 DEG C~180 DEG C are reacted 10~14 hours
(2) product that hydro-thermal reaction obtains is washed with water repeatedly, filter until filtrate liquid be in neutrality (detection of PH test paper),
Then washed product is dehydrated for dry at least 24 hours in vacuum freeze-drying machine to complete
(3) with 5 DEG C/min of heating rate, it is warming up to 450 DEG C under the nitrogen protection of flowing, dry product is moved back
Fire 2.5 hours, cools to room temperature with the furnace, obtains graphene-supported palladium (Pd-rGO) anode composite catalyst.
The structure and performance characterization of the graphene-supported palladium of gained (Pd-rGO) anode composite catalyst: Fig. 1 is our legal system
The X-ray diffractogram (XRD) of standby graphene-supported palladium (Pd-rGO) composite material and pure graphene (rGO) comparison.Fig. 2 is this
Graphene-supported palladium (Pd-rGO) composite catalyst and pure graphene (rGO) of method preparation are catalyzed lithium-air battery 200mA/g
Polarize comparison under current density.Fig. 3 is graphene-supported palladium (Pd-rGO) composite catalyst and pure graphene of this method preparation
(rGO) it is catalyzed capacity cutoff under lithium-air battery 1A/g current densities and recycles comparison diagram.Fig. 4 is that the graphene of this method preparation is negative
Carry specific discharge capacity comparison diagram of palladium (Pd-rGO) the composite catalyst catalysis lithium-air battery under different multiplying.Embodiment two:
(1) 15mL 5mg/mL is added to dilute in 60mL deionized water by the graphene oxide solution that Hummers method obtains
It releases, ultrasonic 30min is uniformly dispersed.Add the RuCl of 5mL 2.3mg/mL3·3H2O aqueous solution.Ultrasonic 15min is uniformly dispersed,
Stirring 8~12 hours.The hydrazine hydrate solution of 5mL 70~85% is added dropwise in the homogenate that will be stirred, and stirs 15min, is transferred to
In the hydrothermal reaction kettle of polytetrafluoro liner.160 DEG C~180 DEG C are reacted 10~14 hours
(2) product that hydro-thermal reaction obtains is washed with water repeatedly, filter until filtrate liquid be in neutrality (detection of PH test paper),
Then washed product is dehydrated for dry at least 24 hours in vacuum freeze-drying machine to complete
(3) with 5 DEG C/min of heating rate, it is warming up to 400 DEG C under the nitrogen protection of flowing, dry product is moved back
Fire 3 hours, cools to room temperature with the furnace, obtains graphene-supported ruthenium (Ru-rGO) anode composite catalyst.
Embodiment three:
(1) 15mL 5.6mg/mL is added to dilute in 60mL deionized water by the graphene oxide solution that Hummers method obtains
It releases, ultrasonic 30min is uniformly dispersed.Add the PdCl of 5mL 1.7mg/mL2Aqueous solution.Ultrasonic 15min is uniformly dispersed, stirring 8
~12 hours.The hydrazine hydrate solution of 5mL 70~85% is added dropwise in the homogenate that will be stirred, and stirs 15min, is transferred to poly- four
In the hydrothermal reaction kettle of fluorine liner.160 DEG C~180 DEG C are reacted 10~14 hours
(2) product that hydro-thermal reaction obtains is washed with water repeatedly, filter until filtrate liquid be in neutrality (detection of PH test paper),
Then washed product is dehydrated for dry at least 24 hours in vacuum freeze-drying machine to complete
(3) with 3 DEG C/min of heating rate, it is warming up to 600 DEG C under the nitrogen protection of flowing, dry product is moved back
Fire 1 hour, cools to room temperature with the furnace, obtains graphene-supported palladium (Pd-rGO) anode composite catalyst.
Example IV:
(1) 15mL 5.6mg/mL is added to dilute in 60mL deionized water by the graphene oxide solution that Hummers method obtains
It releases, ultrasonic 30min is uniformly dispersed.Add the RuCl of 5mL 2.3mg/mL3·3H2O aqueous solution.Ultrasonic 15min is uniformly dispersed,
Stirring 8~12 hours.The hydrazine hydrate solution of 5mL 70~85% is added dropwise in the homogenate that will be stirred, and stirs 15min, is transferred to
In the hydrothermal reaction kettle of polytetrafluoro liner.160 DEG C~180 DEG C are reacted 10~14 hours
(2) product that hydro-thermal reaction obtains is washed with water repeatedly, filter until filtrate liquid be in neutrality (detection of PH test paper),
Then washed product is dehydrated for dry at least 24 hours in vacuum freeze-drying machine to complete
(3) with 3 DEG C/min of heating rate, it is warming up to 600 DEG C under the nitrogen protection of flowing, dry product is moved back
Fire 1 hour, cools to room temperature with the furnace, obtains graphene-supported ruthenium (Ru-rGO) anode composite catalyst.
Embodiment five:
(1) 15mL 5mg/mL is added to dilute in 60mL deionized water by the graphene oxide solution that Hummers method obtains
It releases, ultrasonic 30min is uniformly dispersed.Add the PdCl of 5mL 0.8mg/mL2Aqueous solution.Ultrasonic 15min is uniformly dispersed, stirring 8
~12 hours.The hydrazine hydrate solution of 5mL 70~85% is added dropwise in the homogenate that will be stirred, and stirs 15min, is transferred to poly- four
In the hydrothermal reaction kettle of fluorine liner.160 DEG C~180 DEG C are reacted 10~14 hours
(2) product that hydro-thermal reaction obtains is washed with water repeatedly, filter until filtrate liquid be in neutrality (detection of PH test paper),
Then washed product is dehydrated for dry at least 24 hours in vacuum freeze-drying machine to complete
(3) with 5 DEG C/min of heating rate, it is warming up to 400 DEG C under the nitrogen protection of flowing, dry product is moved back
Fire 3 hours, cools to room temperature with the furnace, obtains graphene-supported palladium (Pd-rGO) anode composite catalyst.
Embodiment six:
(1) the oxide/carbon nanometer tube solution that 15mL 5.6mg/mL is obtained by Hummers method is added in 60mL deionized water
Dilution, ultrasonic 30min are uniformly dispersed.Add the PdCl of 5mL 1.7mg/mL2Aqueous solution.Ultrasonic 15min is uniformly dispersed, stirring
8~12 hours.The hydrazine hydrate solution of 5mL 70~85% is added dropwise in the homogenate that will be stirred, and stirs 15min, is transferred to poly- four
In the hydrothermal reaction kettle of fluorine liner.160 DEG C~180 DEG C are reacted 10~14 hours
(2) product that hydro-thermal reaction obtains is washed with water repeatedly, filter until filtrate liquid be in neutrality (detection of PH test paper),
Then washed product is dehydrated for dry at least 24 hours in vacuum freeze-drying machine to complete
(3) with 5 DEG C/min of heating rate, it is warming up to 400 DEG C under the nitrogen protection of flowing, dry product is moved back
Fire 3 hours, cools to room temperature with the furnace, obtains graphene-supported palladium (Pd-rGO) anode composite catalyst.
Embodiment seven:
(1) the oxide/carbon nanometer tube solution that 15mL 5.6mg/mL is obtained by Hummers method is added in 60mL deionized water
Dilution, ultrasonic 30min are uniformly dispersed.Add 5mL 2.5mg/mL hydrate ruthenium trichloride (RuCl3·3H2O).Ultrasonic 15min points
It dissipates uniformly, stirs 8~12 hours.The hydrazine hydrate solution of 5mL 70~85% is added dropwise in the homogenate that will be stirred, stirring
15min is transferred in the hydrothermal reaction kettle of polytetrafluoro liner.160 DEG C~180 DEG C are reacted 10~14 hours
(2) product that hydro-thermal reaction obtains is washed with water repeatedly, filter until filtrate liquid be in neutrality (detection of PH test paper),
Then washed product is dehydrated for dry at least 24 hours in vacuum freeze-drying machine to complete
(3) with 5 DEG C/min of heating rate, it is warming up to 400 DEG C under the nitrogen protection of flowing, dry product is moved back
Fire 3 hours, cools to room temperature with the furnace, obtains graphene-supported ruthenium (Ru-rGO) anode composite catalyst.
Embodiment eight:
(1) the oxide/carbon nanometer tube solution that 15mL 5mg/mL is obtained by Hummers method is added to dilute in 60mL deionized water
It releases, ultrasonic 30min is uniformly dispersed.Add the RuCl of 5mL 2.3mg/mL3·3H2O aqueous solution.Ultrasonic 15min is uniformly dispersed,
Stirring 8~12 hours.The hydrazine hydrate solution of 5mL 70~85% is added dropwise in the homogenate that will be stirred, and stirs 15min, is transferred to
In the hydrothermal reaction kettle of polytetrafluoro liner.160 DEG C~180 DEG C are reacted 10~14 hours.
(2) product that hydro-thermal reaction obtains is washed with water repeatedly, filter until filtrate liquid be in neutrality (detection of PH test paper),
Then washed product is dehydrated for dry at least 24 hours in vacuum freeze-drying machine to complete.
(3) with 5 DEG C/min of heating rate, it is warming up to 450 DEG C under the nitrogen protection of flowing, dry product is moved back
Fire 2.5 hours, cools to room temperature with the furnace, obtains graphene-supported ruthenium (Ru-rGO) anode composite catalyst.
Embodiment nine:
(1) the oxide/carbon nanometer tube solution that 15mL 5mg/mL is obtained by Hummers method is added to dilute in 60mL deionized water
It releases, ultrasonic 30min is uniformly dispersed.Add the PdCl of 5mL 1.5mg/mL2Aqueous solution.Ultrasonic 15min is uniformly dispersed, stirring 8
~12 hours.The hydrazine hydrate solution of 5mL 70~85% is added dropwise in the homogenate that will be stirred, and stirs 15min, is transferred to poly- four
In the hydrothermal reaction kettle of fluorine liner.160 DEG C~180 DEG C are reacted 10~14 hours
(2) product that hydro-thermal reaction obtains is washed with water repeatedly, filter until filtrate liquid be in neutrality (detection of PH test paper),
Then washed product is dehydrated for dry at least 24 hours in vacuum freeze-drying machine to complete
(3) with 4 DEG C/min of heating rate, it is warming up to 600 DEG C under the nitrogen protection of flowing, dry product is moved back
Fire 1.2 hours, cools to room temperature with the furnace, obtains Pd-rGO anode composite catalyst.
Embodiment ten:
(1) the oxide/carbon nanometer tube solution that 15mL 5mg/mL is obtained by Hummers method is added to dilute in 60mL deionized water
It releases, ultrasonic 30min is uniformly dispersed.Add the PdCl of 5mL 0.8mg/mL2Aqueous solution.Ultrasonic 15min is uniformly dispersed, stirring 8
~12 hours.The hydrazine hydrate solution of 5mL 70~85% is added dropwise in the homogenate that will be stirred, and stirs 15min, is transferred to poly- four
In the hydrothermal reaction kettle of fluorine liner.160 DEG C~180 DEG C are reacted 10~14 hours
(2) product that hydro-thermal reaction obtains is washed with water repeatedly, filter until filtrate liquid be in neutrality (detection of PH test paper),
Then washed product is dehydrated for dry at least 24 hours in vacuum freeze-drying machine to complete
(3) with 4 DEG C/min of heating rate, it is warming up to 600 DEG C under the nitrogen protection of flowing, dry product is moved back
Fire 1.2 hours, cools to room temperature with the furnace, obtains graphene-supported palladium (Pd-rGO) anode composite catalyst.
Application example:
(1) by graphene-supported palladium (Pd-rGO) composite catalyst wherein prepared with being assembled into mold lithium-air battery；
(2) capacity is carried out to battery performance under the discharge current density of 200mA/g and ends charge and discharge, with pure graphene
(rGO) catalyst is compared, and voltage polarizing is substantially reduced, as shown in Figure 2；
(3) capacity cutoff charge-discharge test, charge and discharge cycles are carried out to battery performance under the discharge current density of 1A/g
100 circles, compared with pure graphene (rGO) catalyst, cyclical stability is significantly improved, as shown in Figure 3；
(4) in 100mA/g, 200mA/g, 400mA/g, 1A/g, under 2A/g discharge current density to battery high rate performance into
Row test, as a result as shown in figure 4, graphene-supported palladium (Pd-rGO) composite catalyst kept during high rate charge-discharge compared with
High capacity.
Claims (1)
1. a kind of preparation method of hypopolarization lithium-air battery anode catalytic material, it is characterised in that this method includes following step
It is rapid:
(1) 15mL concentration is 5~10mg/mL graphene oxide solution or receives the carbonoxide that 15mL concentration is 5~10mg/mL
Mitron solution, which is added in 60mL deionized water, to be diluted, and ultrasonication 30 minutes, is uniformly dispersed；Adding 5mL concentration is
The palladium chloride aqueous solution or 5mL concentration of 0.8-2.0mg/mL is the hydrate ruthenium trichloride of 1.0-2.5mg/mL, is ultrasonically treated 15 points
Clock is uniformly dispersed, and stirs 8~12 hours, obtains even incite somebody to action；By 5mL mass percentage concentration be 70~85% hydrazine hydrate solution dropwise
It is added in the homogenate being stirred, stirs 15 minutes, be transferred in the hydrothermal reaction kettle of polytetrafluoro liner, it is anti-at 160 DEG C~180 DEG C
It answers 10~14 hours, obtains reaction product；
(2) reaction product of above-mentioned steps (1) is washed with water repeatedly, filtered, until solution is in neutrality, it then will be washed
Product is 20~26 hours dry in vacuum freeze-drying machine, until dehydration completely, obtains desciccate；
(3) with 3 DEG C~5 DEG C/min of heating rate, it is warming up to 400~600 DEG C under the nitrogen protection of flowing, is produced dry
Object is annealed 1~3 hour, is cooled to room temperature with the furnace, is obtained hypopolarization lithium-air battery anode catalytic material.
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