CN103219527A - Air electrode for lithium-air battery and preparation method for air electrode - Google Patents
Air electrode for lithium-air battery and preparation method for air electrode Download PDFInfo
- Publication number
- CN103219527A CN103219527A CN2013101278804A CN201310127880A CN103219527A CN 103219527 A CN103219527 A CN 103219527A CN 2013101278804 A CN2013101278804 A CN 2013101278804A CN 201310127880 A CN201310127880 A CN 201310127880A CN 103219527 A CN103219527 A CN 103219527A
- Authority
- CN
- China
- Prior art keywords
- air electrode
- preparation
- silicon ball
- lithium
- air
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention relates to an air electrode for a lithium-air battery and a preparation method for the air electrode, which belong to the field of electrochemical energy materials, and aim to solve the technical problems of high overpotential, low charging and discharging utilization rate and few cycle times of a lithium-air battery in the prior art. The air electrode for the lithium-air battery is made of a nanocrystalline catalyst-modified hollow carbon sphere and carbon paper air electrode material with a hierarchical porous structure. When the air electrode is used for the lithium-air battery, the specific energy, energy utilization efficiency, rate capability and cycling stability of the lithium-air battery can be effectively improved, and particularly, the cycle life of the lithium-air battery is prolonged to 205 times from conventional maximum 100 times reported by documents. According to the preparation method for the air electrode, a hard template method and an electrophoretic technology are reasonably combined, a process is simple, the operation is convenient, the cost is low, an additive is avoided, a complex powder electrode preparation process is eliminated, and the stability of an air positive electrode is greatly improved.
Description
Technical field
The present invention relates to electrochemical energy material technology field, particularly a kind of lithium-air battery air electrode and preparation method thereof.
Background technology
Lithium-air battery is subjected to extensive concern owing to having the high theoretical energy density, but wants it realize is used, and also needs to solve a series of problems, such as the overpotential height, discharge and recharge and utilize shortcomings such as rate variance, cycle-index are few.Lithium-air battery is when work, and oxygen at first becomes O at the anodal surface reduction of porous carbon air
2 -, then with electrolyte in Li
+In conjunction with generating product Li
2O
2Because discharging product Li
2O
2Therefore can not be dissolved in the organic electrolyte, can only deposit having on the air positive pole of negative oxygen ion.And the porous carbon air positive pole that uses at present all obtains with material with carbon element accumulation pore-creating, and low, connective difference of the utilance in duct and mass transfer ability make discharging product Li
2O
2Limited storage space, directly cause the overpotential height of lithium-air battery, discharge and recharge and utilize rate variance and cycle-index few.On the other hand, the mode of mechanical mixture is mainly still adopted in the load of hydrogen reduction in the existing porous carbon air positive pole/separate out catalyst, the cooperative effect between carrier and the catalyst be can not effectively bring into play, lithium-air battery energy conversion efficiency and high rate performance further worsened.
Summary of the invention
The present invention will solve lithium-air battery overpotential height in the prior art, discharge and recharge and utilize rate variance and the few technical problem of cycle-index, a kind of multi-stage artery structure is provided, catalyst is modified at absolute construction on the electrode, and lithium-air battery is with air electrode and preparation method thereof.
In order to solve the problems of the technologies described above, technical scheme of the present invention is specific as follows:
A kind of lithium-air battery air electrode, this air electrode is a multi-stage artery structure, the hollow carbon sphere carbon paper air electrode material that nanocrystalline catalyst is modified, on the inwall of nanocrystalline catalyst attached to hollow carbon sphere, hollow carbon sphere is present in the network space of carbon paper; Wherein, nanocrystalline catalyst is noble metal or transition metal oxide.
In technique scheme, described noble metal is palladium, platinum or gold; Described transition metal oxide is manganese dioxide, cobaltosic oxide or di-iron trioxide.
In technique scheme, the spherical shell internal diameter of the hollow carbon sphere of described air electrode material is 0.1～10 μ m.
In technique scheme, the wall thickness of the hollow carbon sphere of described air electrode material is 3～30nm.
In technique scheme, the load capacity of nanocrystalline catalyst is 5～40% in the described air electrode material.
A kind of lithium-air battery preparation method of air electrode, this preparation method mainly may further comprise the steps:
(1) adopts
Legal system is equipped with high dispersive silicon ball;
(2) with sulfhydrylization reagent and above-mentioned silicon ball, obtain sulfhydrylation silicon ball after the back flow reaction;
(3) with sulfhydrylation silicon ball electrophoresis in the network space of carbon paper, obtain sulfhydrylation silicon ball carbon paper electrode;
(4) above-mentioned sulfhydrylation silicon ball carbon paper electrode is immersed in the presoma salting liquid of noble metal or transition metal oxide, filter, oven dry is under the protection of argon hydrogen mixed atmosphere, in 200～350 ℃ temperature lower calcinations 1～3 hour, obtain nanocrystalline catalyst-silicon ball carbon paper compound;
(5) above-mentioned nanocrystalline catalyst-silicon ball carbon paper compound is soaked in 10～30% contain in the carbon solution, filter drying; under nitrogen protection; in 800～850 ℃ temperature lower calcinations 1～3 hour, obtain multi-stage artery structure, hollow carbon sphere carbon paper air electrode that nanocrystalline catalyst is modified.
Wherein, the carbon solution that contains described in the step (5) is sucrose, glucose, phenolic resins, furfuryl alcohol, styrene or cyclodextrin solution.
In technique scheme, the presoma salting liquid of described noble metal is the acetylacetone,2,4-pentanedione solution of palladium, platinum or gold; The presoma salting liquid of described transition metal oxide is the nitrate or the acetate solution of manganese dioxide, cobaltosic oxide or di-iron trioxide.
In technique scheme, the concrete preparation method of described step (1) is: join concentrated ammonia liquor, ethanol, deionized water and tetraethoxysilane in the round-bottomed flask successively, stirred 5～18 hours, the product that obtains is obtained high dispersive silicon ball by centrifugation, washing and dry under 100 ℃ of conditions.
In technique scheme, the volume ratio of described concentrated ammonia liquor, ethanol, deionized water and tetraethoxysilane is 1:(10-20): (1-5): (1-2).
In technique scheme, the concrete preparation method of described step (2) is: sulfhydrylization reagent and silicon ball are joined in the toluene successively, and 110 ℃ were refluxed 10～20 hours, and room temperature cooling then, centrifugal, washing, oven dry obtain sulfhydrylation silicon ball.
In technique scheme, described sulfhydrylization reagent is mercaptoethanol, 3-sulfydryl propyl trimethoxy silicane or mercaptopropionic acid.
In technique scheme, the concrete preparation method of described step (3) is: two electrodes are respectively carbon paper and steel disc, electrode spacing is 0.5～2.0cm, electrolyte is that sulfhydrylation silicon ball is scattered in acetone and the methanol mixed solvent, electrophoretic voltage is 15～25V, obtains sulfhydrylation silicon ball carbon paper electrode.
In technique scheme, the volume ratio of described acetone and methyl alcohol is 1:(0.1-10).
In technique scheme, in the described argon hydrogen of step (4) gaseous mixture, hydrogen and argon content are respectively 5% and 95%.
A kind of lithium-air battery of the present invention has following beneficial effect with air electrode and preparation method thereof:
1, a kind of lithium-air battery air electrode provided by the invention is the hollow carbon sphere carbon paper integrated electrode with nanocrystalline catalyst modification of multi-stage artery structure, is the absolute construction that nanocrystalline catalyst is modified at the inwall of hollow carbon sphere.The nanocrystalline catalyst and the micropore of air electrode of the present invention provide catalytic site; Intercommunicating pore between the spherical shell provides the transmission channel of oxygen and electrolyte; Macropore (empty spherical shell) provides solid discharging product Li
2O
2The place that deposits/deviate from.As Fig. 1 is the FESEM figure of the hollow carbon sphere carbon paper air electrode modified of the palladium of the embodiment of the invention one preparation.This figure can illustrate that air electrode material of the present invention has multi-stage artery structure.Fig. 2 is the nitrogen adsorption curve and the graph of pore diameter distribution of the hollow carbon sphere carbon paper air electrode modified of the palladium of the embodiment of the invention one preparation.This figure can illustrate that air electrode material of the present invention has multi-stage artery structures such as micropore, mesoporous and macropore.
2, lithium-air battery provided by the invention with preparation method's reasonable combination of air electrode hard template method and electrophoretic techniques; its technology is simple, easy to operate, cost is low, easily accomplish scale production; and do not need to add binding agent; save complicated powder electrode preparation process, significantly improved the stability of air positive pole.When the air electrode of this method preparation is used for lithium-air battery, can effectively improve specific energy, energy utilization efficiency, high rate performance and the cyclical stability etc. of lithium-air battery.Wherein, the more commercial carbon air electrode of high rate performance has improved 37 times, cyclical stability and has improved 5 times, overpotential and bring up to 77% by 60%, and especially cycle life significantly is increased to 205 times from the longest 100 times of present bibliographical information.The hollow carbon sphere carbon paper air electrode that Fig. 3 modifies for the palladium of the embodiment of the invention one preparation is used for the charging and discharging curve of lithium-air battery, and limit capacity is 1000mAh g
-1, current density is 300mA g
-1This figure can illustrate that the lithium-air battery cycle performance that includes air electrode of the present invention reaches 205 times, is 2 times of present 100 times best in the world circulations of reporting.The hollow carbon sphere carbon paper air electrode that Fig. 4 modifies for the palladium of present embodiment one preparation is used for the cycle performance curve of lithium-air battery, and limit capacity is 1000mAh g
-1, current density is 300mA g
-1This figure can illustrate the increase not significantly reduction of the discharge voltage of the lithium-air battery that includes air electrode of the present invention along with cycle-index.
Description of drawings
Fig. 1 is the FESEM figure of the hollow carbon sphere carbon paper air electrode modified of the palladium of the embodiment of the invention one preparation.
Fig. 2 is the nitrogen adsorption curve and the graph of pore diameter distribution of the hollow carbon sphere carbon paper air electrode modified of the palladium of the embodiment of the invention one preparation.
The hollow carbon sphere carbon paper air electrode that Fig. 3 modifies for the palladium of the embodiment of the invention one preparation is used for the charging and discharging curve of lithium-air battery, and limit capacity is 1000mAh g
-1, current density is 300mA g
-1
The hollow carbon sphere carbon paper air electrode that Fig. 4 modifies for the palladium of the embodiment of the invention one preparation is used for the cycle performance curve of lithium-air battery, and limit capacity is 1000mAh g
-1, current density is 300mA g
-1
Embodiment
A kind of lithium-air battery air electrode provided by the invention, this air electrode are the hollow carbon sphere carbon paper electrode material that the nanocrystalline catalyst of multi-stage artery structure is modified, and on the inwall of nanocrystalline catalyst attached to hollow carbon sphere, its load capacity is 5～40%; Hollow carbon sphere is present in the network space of carbon paper, and the spherical shell internal diameter is 0.1～10 μ m, and the wall thickness of hollow carbon sphere is 3～30nm.Wherein, nanocrystalline catalyst is noble metal or transition metal oxide.Can be palladium, platinum or gold as noble metal; Transition metal oxide can be manganese dioxide, cobaltosic oxide or di-iron trioxide.
Lithium-air battery air electrode of the present invention is prepared by following method:
(1) adopts
Legal system is equipped with high dispersive silicon ball
Concentrated ammonia liquor, ethanol, deionized water and tetraethoxysilane are joined in the round-bottomed flask successively, stirred 5～18 hours, the product that obtains is obtained high dispersive silicon ball by centrifugation, washing and dry under 100 ℃ of conditions.
The volume ratio of described concentrated ammonia liquor, ethanol, deionized water and tetraethoxysilane is 1:(10-20): (1-5): (1-2).
(2) silicon ball sulfhydrylation
Sulfhydrylization reagent and silicon ball are joined in the toluene successively, and 110 ℃ were refluxed 10～20 hours, and room temperature cooling then, centrifugal, washing, oven dry obtain sulfhydrylation silicon ball.
Described sulfhydrylization reagent is mercaptoethanol, 3-sulfydryl propyl trimethoxy silicane or mercaptopropionic acid.
(3) with sulfhydrylation silicon ball electrophoresis in the network space of carbon paper
Two electrodes are respectively carbon paper and steel disc, and electrode spacing is 0.5～2.0cm, and electrolyte is that sulfhydrylation silicon ball is scattered in acetone and the methanol mixed solvent, and electrophoretic voltage is 15～25V, obtains sulfhydrylation silicon ball carbon paper electrode.
The volume ratio of described acetone and methyl alcohol is 1:(0.1-10).
(4) above-mentioned sulfhydrylation silicon ball carbon paper electrode is immersed in the presoma salting liquid of noble metal or transition metal oxide, filter, oven dry, under argon hydrogen mixed atmosphere (hydrogen 5%) protection, in 200～350 ℃ temperature lower calcinations 1～3 hour, obtain nanocrystalline catalyst-silicon ball carbon paper compound;
The presoma salting liquid of described noble metal is the acetylacetone,2,4-pentanedione solution of palladium, platinum or gold; The presoma salting liquid of described transition metal oxide is the nitrate or the acetate of manganese dioxide, cobaltosic oxide or di-iron trioxide.
(5) above-mentioned nanocrystalline catalyst-silicon ball carbon paper compound is soaked in 10～30% contain in the carbon solution; filter, drying is under nitrogen protection; in 800～850 ℃ temperature lower calcinations 1～3 hour, obtain the hollow carbon sphere carbon paper air electrode that nanocrystalline catalyst is modified.
Wherein, the carbon solution that contains described in the step (5) is sucrose, glucose, phenolic resins, furfuryl alcohol, styrene or cyclodextrin solution.
Embodiment one
(1) 15mL concentrated ammonia liquor, 150mL ethanol and 15mL deionized water, 15mL tetraethoxysilane are joined successively in the round-bottomed flask and to stir 5 hours, the product that obtains is obtained high dispersive silicon ball by centrifugation, washing and dry under 100 ℃ of conditions.
(2) 6mL3-sulfydryl propyl trimethoxy silicane and 2.0g silicon ball join in the 200mL toluene successively, and 110 ℃ were refluxed 10 hours, and room temperature cooling then, centrifugal, washing, oven dry obtain sulfhydrylation silicon ball.
(3) two electrodes are respectively carbon paper and steel disc, and electrode spacing is 0.5cm, and electrolyte is that sulfhydrylation silicon ball is scattered in the acetone and methanol mixed solvent that volume ratio is 1:1, and electrophoretic voltage is 15V, obtains sulfhydrylation silicon ball carbon paper electrode.
(4) sulfhydrylation silicon ball carbon paper electrode is immersed in half an hour in the chloroformic solution that mass concentration is 5% palladium acetylacetonate, filters, oven dry, 300 ℃ of calcinings are 1 hour under argon hydrogen mixed atmosphere (hydrogen 5%) protection, obtain palladium-silicon ball carbon paper compound.
(5) palladium-silicon ball carbon paper compound is soaked into half an hour in 10% sucrose solution, filter, dry, 850 ℃ of calcinings 3 hours under nitrogen protection, obtain the hollow carbon sphere carbon paper air electrode that palladium is modified.
Fig. 1 is the FESEM figure of the hollow carbon sphere carbon paper air electrode modified of the palladium of present embodiment one preparation.As seen from the figure, this air electrode material has multi-stage artery structure, and empty spherical shell provides the transmission channel that lithium peroxide memory space, intercommunicating pore provide electrolyte and oxygen, the deposition behavior that catalyst is regulated discharging product.
Fig. 2 is the nitrogen adsorption curve and the graph of pore diameter distribution of the hollow carbon sphere carbon paper air electrode modified of the palladium of present embodiment one preparation.As seen from the figure, this air electrode material has multi-stage artery structures such as micropore, mesoporous and macropore.
The hollow carbon sphere carbon paper air electrode that Fig. 3 modifies for the palladium of present embodiment one preparation is used for the charging and discharging curve of lithium-air battery, and limit capacity is 1000mAh g
-1, current density is 300mA g
-1As seen from the figure, the lithium-air battery cycle performance that includes the present embodiment air electrode reaches 205 times, is 2 times of present 100 times best in the world circulations of reporting.
The hollow carbon sphere carbon paper air electrode that Fig. 4 modifies for the palladium of present embodiment one preparation is used for the cycle performance curve of lithium-air battery, and limit capacity is 1000mAh g
-1, current density is 300mA g
-1As seen from the figure, the discharge voltage that includes the lithium-air battery of present embodiment air electrode does not reduce along with the increase of cycle-index is tangible.
Embodiment two
(1) 15mL concentrated ammonia liquor, 300mL ethanol and 75mL deionized water, 30mL tetraethoxysilane are joined successively in the round-bottomed flask and to stir 10 hours, the product that obtains is obtained high dispersive silicon ball by centrifugation, washing and dry under 100 ℃ of conditions.
(2) 30mL mercaptopropionic acid and 2.0g silicon ball join in the 200mL toluene successively, and 110 ℃ were refluxed 12 hours, and room temperature cooling then, centrifugal, washing, oven dry obtain sulfhydrylation silicon ball.
(3) two electrodes are respectively carbon paper and steel disc, and electrode spacing is 2.0cm, and electrolyte is that sulfhydrylation silicon ball is scattered in the acetone and methanol mixed solvent that volume ratio is 10:1, and electrophoretic voltage is 25V, obtains sulfhydrylation silicon ball carbon paper electrode.
(4) sulfhydrylation silicon ball carbon paper electrode being immersed in mass concentration is half an hour in 20% the chlorauric acid solution, filters, oven dry, and 200 ℃ of calcinings are 3 hours under argon hydrogen mixed atmosphere (hydrogen 5%) protection, obtain gold-hollow silicon ball carbon paper compound.
(5) gold-silicon ball carbon paper compound is soaked into half an hour in 15% glucose solution, filter, dry, 800 ℃ of calcinings 3 hours under nitrogen protection, obtain the hollow carbon sphere carbon paper air electrode that gold is modified.
Embodiment three
(1) 15mL concentrated ammonia liquor, 200mL ethanol and 45mL deionized water, 15mL tetraethoxysilane are joined successively in the round-bottomed flask and to stir 18 hours, the product that obtains is by centrifugation, washing and dry under 100 ℃ of conditions.
(2) 20mL mercaptoethanol and 2.0g silicon ball join in the 200mL toluene successively, and 110 ℃ were refluxed 15 hours, and room temperature cooling then, centrifugal, washing, oven dry obtain sulfhydrylation silicon ball.
(3) two electrodes are respectively carbon paper and steel disc, and electrode spacing is 1.0cm, and electrolyte is that sulfhydrylation silicon ball is scattered in the acetone and methanol mixed solvent that volume ratio is 1:10, and electrophoretic voltage is 20V, obtains sulfhydrylation silicon ball carbon paper electrode.
(4) sulfhydrylation silicon ball carbon paper electrode being immersed in mass concentration is half an hour in 8% the manganese acetate solution, filters, oven dry, and 350 ℃ of calcinings are 3 hours under argon hydrogen mixed atmosphere (hydrogen 5%) protection, obtain manganese dioxide-silicon ball carbon paper compound.
(5) manganese dioxide-silicon ball carbon paper compound is soaked into half an hour in 30% phenol resin solution, filter, dry, 850 ℃ of calcinings 1 hour under nitrogen protection, obtain the hollow carbon sphere carbon paper air electrode that manganese dioxide is modified.
Embodiment four
(1) 15mL concentrated ammonia liquor, 200mL ethanol and 15mL deionized water, 18mL tetraethoxysilane are joined successively in the round-bottomed flask and to stir 18 hours, the product that obtains is by centrifugation, washing and dry under 100 ℃ of conditions.
(2) 15mL3-sulfydryl propyl trimethoxy silicane and 2.0g silicon ball join in the 200mL toluene successively, and 110 ℃ were refluxed 20 hours, and room temperature cooling then, centrifugal, washing, oven dry obtain sulfhydrylation silicon ball.
(3) two electrodes are respectively carbon paper and steel disc, and electrode spacing is 1.5cm, and electrolyte is that sulfhydrylation silicon ball is scattered in the acetone and methanol mixed solvent that volume ratio is 1:2, and electrophoretic voltage is 15V, obtains sulfhydrylation silicon ball carbon paper electrode.
(4) sulfhydrylation silicon ball carbon paper electrode being immersed in mass concentration is half an hour in 12% the iron nitrate solution, filters, oven dry, and 350 ℃ of calcinings obtained di-iron trioxide-silicon ball carbon paper compound after 1 hour under argon hydrogen mixed atmosphere (hydrogen 5%) protection.
(5) di-iron trioxide-silicon ball carbon paper compound is soaked into half an hour in 20% furfuryl alcohol solution, filter, dry, 850 ℃ of calcinings 1 hour under nitrogen protection, obtain the hollow carbon sphere carbon paper air electrode that di-iron trioxide is modified.
Embodiment five
(1) 15mL concentrated ammonia liquor, 300mL ethanol and 75mL deionized water, 30mL tetraethoxysilane are joined successively in the round-bottomed flask and to stir 10 hours, the product that obtains is obtained high dispersive silicon ball by centrifugation, washing and dry under 100 ℃ of conditions.
(2) 30mL3-sulfydryl propyl trimethoxy silicane and 2.0g silicon ball join in the 200mL toluene successively, and 110 ℃ were refluxed 12 hours, and room temperature cooling then, centrifugal, washing, oven dry obtain sulfhydrylation silicon ball.
(3) two electrodes are respectively carbon paper and steel disc, and electrode spacing is 2.0cm, and electrolyte is that sulfhydrylation silicon ball is scattered in the acetone and methanol mixed solvent that volume ratio is 10:1, and electrophoretic voltage is 25V, obtains sulfhydrylation silicon ball carbon paper electrode.
(4) sulfhydrylation silicon ball carbon paper electrode being immersed in mass concentration is half an hour in 20% the acetylacetone,2,4-pentanedione platinum solution, filters, oven dry, and 200 ℃ of calcinings are 3 hours under argon hydrogen mixed atmosphere (hydrogen 5%) protection, obtain platinum-silicon ball carbon paper compound.
(5) platinum-silicon ball carbon paper compound is soaked into half an hour in 15% styrene solution, filter, dry, 800 ℃ of calcinings 3 hours under nitrogen protection, obtain the hollow carbon sphere carbon paper air electrode that platinum is modified.
Embodiment six
(1) 15mL concentrated ammonia liquor, 200mL ethanol and 15mL deionized water, 18mL tetraethoxysilane are joined successively in the round-bottomed flask and to stir 18 hours, the product that obtains is obtained high dispersive silicon ball by centrifugation, washing and dry under 100 ℃ of conditions.
(2) 15mL3-sulfydryl propyl trimethoxy silicane and 2.0g silicon ball join in the 200mL toluene successively, and 110 ℃ were refluxed 20 hours, and room temperature cooling then, centrifugal, washing, oven dry obtain sulfhydrylation silicon ball.
(3) two electrodes are respectively carbon paper and steel disc, and electrode spacing is 1.5cm, and electrolyte is that sulfhydrylation silicon ball is scattered in the acetone and methanol mixed solvent that volume ratio is 1:2, and electrophoretic voltage is 15V, obtains sulfhydrylation silicon ball carbon paper electrode.
(4) sulfhydrylation silicon ball carbon paper electrode being immersed in mass concentration is half an hour in 15% the cobalt nitrate solution, filters, oven dry, and 350 ℃ of calcinings are 1 hour under argon hydrogen mixed atmosphere (hydrogen 5%) protection, obtain cobaltosic oxide-silicon ball carbon paper compound.
(5) cobaltosic oxide-silicon ball carbon paper compound is soaked into half an hour in 20% cyclodextrin solution, filter, dry, 850 ℃ of calcinings 1 hour under nitrogen protection, obtain the hollow carbon sphere carbon paper air electrode that cobaltosic oxide is modified.
Obviously, the foregoing description only is for example clearly is described, and is not the qualification to execution mode.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here need not also can't give exhaustive to all execution modes.And conspicuous variation of being extended out thus or change still are among the protection range of the invention.
Claims (14)
1. lithium-air battery air electrode, it is characterized in that this air electrode is a multi-stage artery structure, the hollow carbon sphere carbon paper air electrode material that nanocrystalline catalyst is modified, on the inwall of nanocrystalline catalyst attached to hollow carbon sphere, hollow carbon sphere is present in the network space of carbon paper; Wherein, nanocrystalline catalyst is noble metal or transition metal oxide.
2. lithium-air battery air electrode according to claim 1 is characterized in that, described noble metal is palladium, platinum or gold; Described transition metal oxide is manganese dioxide, cobaltosic oxide or di-iron trioxide.
3. lithium-air battery air electrode according to claim 1 is characterized in that, the spherical shell internal diameter of the hollow carbon sphere of described air electrode material is 0.1～10 μ m.
4. lithium-air battery air electrode according to claim 1 is characterized in that, the wall thickness of the hollow carbon sphere of described air electrode material is 3～30nm.
5. lithium-air battery air electrode according to claim 1 is characterized in that, the load capacity of nanocrystalline catalyst is 5～40% in the described air electrode material.
6. the lithium-air battery according to claim 1 preparation method of air electrode is characterized in that this preparation method mainly may further comprise the steps:
(1) adopts
Legal system is equipped with high dispersive silicon ball;
(2) with sulfhydrylization reagent and above-mentioned silicon ball, obtain sulfhydrylation silicon ball after the back flow reaction;
(3) with sulfhydrylation silicon ball electrophoresis in the network space of carbon paper, obtain sulfhydrylation silicon ball carbon paper electrode;
(4) above-mentioned sulfhydrylation silicon ball carbon paper electrode is immersed in the presoma salting liquid of noble metal or transition metal oxide, filter, oven dry is under the protection of argon hydrogen mixed atmosphere, in 200～350 ℃ temperature lower calcinations 1～3 hour, obtain nanocrystalline catalyst-silicon ball carbon paper compound;
(5) above-mentioned nanocrystalline catalyst-silicon ball carbon paper compound is soaked in 10～30% contain in the carbon solution, filter drying, under nitrogen protection, in 800～850 ℃ temperature lower calcinations 1～3 hour, obtain multi-stage artery structure, hollow carbon sphere carbon paper air electrode that nanocrystalline catalyst is modified;
Wherein, the carbon solution that contains described in the step (5) is sucrose, glucose, phenolic resins, furfuryl alcohol, styrene or cyclodextrin solution.
7. preparation method according to claim 6 is characterized in that, the presoma salting liquid of described noble metal is the acetylacetone,2,4-pentanedione solution of palladium, platinum or gold; The presoma salting liquid of described transition metal oxide is the nitrate or the acetate solution of manganese dioxide, cobaltosic oxide or di-iron trioxide.
8. preparation method according to claim 6, it is characterized in that, the concrete preparation method of described step (1) is: join concentrated ammonia liquor, ethanol, deionized water and tetraethoxysilane in the round-bottomed flask successively, stirred 5～18 hours, the product that obtains is obtained high dispersive silicon ball by centrifugation, washing and dry under 100 ℃ of conditions.
9. preparation method according to claim 8 is characterized in that, the volume ratio of described concentrated ammonia liquor, ethanol, deionized water and tetraethoxysilane is 1:(10-20): (1-5): (1-2).
10. preparation method according to claim 6, it is characterized in that the concrete preparation method of described step (2) is: sulfhydrylization reagent and silicon ball are joined in the toluene successively, and 110 ℃ were refluxed 10～20 hours, room temperature cooling then, centrifugal, washing, oven dry obtain sulfhydrylation silicon ball.
11. preparation method according to claim 10 is characterized in that, described sulfhydrylization reagent is mercaptoethanol, 3-sulfydryl propyl trimethoxy silicane or mercaptopropionic acid.
12. preparation method according to claim 6, it is characterized in that, the concrete preparation method of described step (3) is: two electrodes are respectively carbon paper and steel disc, electrode spacing is 0.5～2.0cm, electrolyte is that sulfhydrylation silicon ball is scattered in acetone and the methanol mixed solvent, electrophoretic voltage is 15～25V, obtains sulfhydrylation silicon ball carbon paper electrode.
13. preparation method according to claim 12 is characterized in that, the volume ratio of described acetone and methyl alcohol is 1:(0.1-10).
14. preparation method according to claim 6 is characterized in that, in the described argon hydrogen of step (4) gaseous mixture, hydrogen and argon content are respectively 5% and 95%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310127880.4A CN103219527B (en) | 2013-04-12 | 2013-04-12 | Air electrode for lithium-air battery and preparation method for air electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310127880.4A CN103219527B (en) | 2013-04-12 | 2013-04-12 | Air electrode for lithium-air battery and preparation method for air electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103219527A true CN103219527A (en) | 2013-07-24 |
| CN103219527B CN103219527B (en) | 2015-05-20 |
Family
ID=48817130
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310127880.4A Active CN103219527B (en) | 2013-04-12 | 2013-04-12 | Air electrode for lithium-air battery and preparation method for air electrode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103219527B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104425856A (en) * | 2013-09-05 | 2015-03-18 | 铃木株式会社 | Lithium-air battery and positive electrode |
| CN105702967A (en) * | 2014-11-28 | 2016-06-22 | 中国科学院大连化学物理研究所 | Self-supporting air electrode and fabrication method thereof |
| CN106975473A (en) * | 2017-05-27 | 2017-07-25 | 苏州思美特表面材料科技有限公司 | The supported materials catalyst of network structure |
| CN107442111A (en) * | 2016-05-30 | 2017-12-08 | 中国科学院长春应用化学研究所 | Carbon-clad metal nanocube material and preparation method thereof |
| CN110711580A (en) * | 2019-10-13 | 2020-01-21 | 浙江大学 | Preparation method and application of cathode material derived from ferrocene |
| WO2020253843A1 (en) * | 2019-06-21 | 2020-12-24 | 中国科学院上海硅酸盐研究所 | A class of porous metal oxide based electrochemical energy storage materials, preparation method therefor and use thereof |
| CN114597423A (en) * | 2021-11-08 | 2022-06-07 | 北京机械设备研究所 | Air battery, composite air electrode and preparation method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101821897A (en) * | 2008-11-27 | 2010-09-01 | 丰田自动车株式会社 | Air secondary battery |
| CN102208652A (en) * | 2010-08-31 | 2011-10-05 | 中国科学院上海硅酸盐研究所 | Air electrode for lithium air battery and preparation method thereof |
| CN102544522A (en) * | 2012-01-11 | 2012-07-04 | 复旦大学 | Composite air electrode of lithium air cell and preparation method thereof |
| CN102637879A (en) * | 2012-04-09 | 2012-08-15 | 中南大学 | Micro-nano-structure anode material for Li-air battery and preparation method of micro-nano-structure anode material |
| WO2013049460A1 (en) * | 2011-09-28 | 2013-04-04 | Excellatron Solid State, Llc | Lithium oxygen batteries having a carbon cloth current collector and method of producing same |
-
2013
- 2013-04-12 CN CN201310127880.4A patent/CN103219527B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101821897A (en) * | 2008-11-27 | 2010-09-01 | 丰田自动车株式会社 | Air secondary battery |
| CN102208652A (en) * | 2010-08-31 | 2011-10-05 | 中国科学院上海硅酸盐研究所 | Air electrode for lithium air battery and preparation method thereof |
| WO2013049460A1 (en) * | 2011-09-28 | 2013-04-04 | Excellatron Solid State, Llc | Lithium oxygen batteries having a carbon cloth current collector and method of producing same |
| CN102544522A (en) * | 2012-01-11 | 2012-07-04 | 复旦大学 | Composite air electrode of lithium air cell and preparation method thereof |
| CN102637879A (en) * | 2012-04-09 | 2012-08-15 | 中南大学 | Micro-nano-structure anode material for Li-air battery and preparation method of micro-nano-structure anode material |
Non-Patent Citations (3)
| Title |
|---|
| CHANG SUNG PARK等: ""Carbon-sphere/Co3O4 nanocomposite catalysts for effective air electrode in Li/air batteries"", 《JOURNAL OF POWER SOURCES》 * |
| WEI-MING ZHANG等: ""Tin-Nanoparticles Encapsulated in Elastic Holllow Carbon Spheres for High-Performance Anode Material in Lithium-Ion Batteries"", 《ADVANCED MATERIALS》 * |
| ZHONG-LI WANG等: ""Graphene Oxide Gel-Derived, Free-Standing, Hierarchically Porous Carbon for High-Capacity and High-Rate Rechargeable Li-O2 Batteries"", 《ADVANCED FUNCTIONAL MATERIALS》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104425856A (en) * | 2013-09-05 | 2015-03-18 | 铃木株式会社 | Lithium-air battery and positive electrode |
| CN105702967A (en) * | 2014-11-28 | 2016-06-22 | 中国科学院大连化学物理研究所 | Self-supporting air electrode and fabrication method thereof |
| CN105702967B (en) * | 2014-11-28 | 2018-11-27 | 中国科学院大连化学物理研究所 | A kind of self-supporting air electrode and preparation method thereof |
| CN107442111A (en) * | 2016-05-30 | 2017-12-08 | 中国科学院长春应用化学研究所 | Carbon-clad metal nanocube material and preparation method thereof |
| CN107442111B (en) * | 2016-05-30 | 2020-04-07 | 中国科学院长春应用化学研究所 | Carbon-coated metal nanocube material and preparation method thereof |
| CN106975473A (en) * | 2017-05-27 | 2017-07-25 | 苏州思美特表面材料科技有限公司 | The supported materials catalyst of network structure |
| CN106975473B (en) * | 2017-05-27 | 2020-07-10 | 苏州思美特表面材料科技有限公司 | Supported material catalyst with network structure |
| WO2020253843A1 (en) * | 2019-06-21 | 2020-12-24 | 中国科学院上海硅酸盐研究所 | A class of porous metal oxide based electrochemical energy storage materials, preparation method therefor and use thereof |
| CN110711580A (en) * | 2019-10-13 | 2020-01-21 | 浙江大学 | Preparation method and application of cathode material derived from ferrocene |
| CN110711580B (en) * | 2019-10-13 | 2020-08-25 | 浙江大学 | Preparation method and application of cathode material derived from ferrocene |
| CN114597423A (en) * | 2021-11-08 | 2022-06-07 | 北京机械设备研究所 | Air battery, composite air electrode and preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103219527B (en) | 2015-05-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103219527B (en) | Air electrode for lithium-air battery and preparation method for air electrode | |
| CN108365230B (en) | Universal preparation method for active site and air electrode structure combination and application | |
| CN103236519B (en) | Porous carbon base monolith composite material for lithium ion battery, and preparation method thereof | |
| CN103855367B (en) | The porous carbon materials of lithium-air battery positive pole N doping | |
| CN103545536A (en) | Carbon fiber supported metal catalyst as well as preparation method and application thereof | |
| CN106654187B (en) | A method of preparing lithium-air battery cobalt iron oxide/multi-walled carbon nanotube composite catalyst | |
| CN103227334A (en) | Carbon-containing metal catalyst, preparation method and application thereof | |
| CN109065897A (en) | Phosphorus-doped porous carbon-coated cobaltosic oxide oxygen reduction catalyst and preparation method and application thereof | |
| CN106356519A (en) | Preparation method of expanded graphite/silicon@carbon negative electrode material for lithium ion batteries | |
| CN103400970B (en) | Nanometer silicon/graphene lithium ion battery cathode material and preparation method thereof | |
| CN111244470B (en) | Nano composite cathode and preparation and application thereof | |
| CN103887529B (en) | A kind of M1+ M2/ C catalyst and preparation method thereof | |
| CN103418417A (en) | Nonmetal oxygen reduction catalyst and preparation method thereof | |
| CN103022435A (en) | Lithium ion battery silicon-carbon composite negative electrode material and preparation method thereof | |
| CN103915633A (en) | Composite carbon fiber-loaded metal catalyst as well as preparation method and application thereof | |
| CN104600271A (en) | Preparation method of sodium titanate/graphene composite cathode material of sodium ion battery | |
| CN104795575A (en) | Preparation method of high-activity composite electrode material of Co3S4 and graphene | |
| CN104332637B (en) | A kind of noble metal nano particles is carried on the method for preparing catalyst of porous graphene | |
| CN109301186A (en) | A kind of tertiary cathode material and preparation method thereof of cladded type porous structure | |
| CN103236549A (en) | Catalyst material for ether group lithium air battery and preparation method thereof | |
| CN105375029B (en) | A kind of ternary silicates composite positive pole and preparation method thereof | |
| CN104332636B (en) | A kind of preparation method of porous graphene carrying transition metal nano-composite catalyst | |
| CN105406041A (en) | Hollow titanium oxide composite material, and preparation method and application thereof | |
| CN104037423A (en) | Preparation method of porous nickle current collector of lithium ion battery | |
| CN102867966A (en) | Porous micro-sphere post-spinel nitride calcium manganese oxygen compound, and preparation of and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |