CN103219527B - 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
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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 field of material technology, particularly a kind of lithium-air battery air electrode and preparation method thereof.
Background technology
Lithium-air battery is subject to extensive concern owing to having higher theoretical energy density, but wants to be realized application, shortcomings such as also needing to solve series of problems, such as overpotential is high, discharge and recharge utilizes rate variance, cycle-index is few.Operationally, first oxygen become O at porous carbon air cathode surface reduction to lithium-air battery
2 -, then with the Li in electrolyte
+in conjunction with generation product Li
2o
2.Due to discharging product Li
2o
2can not be dissolved in organic electrolyte, therefore can only deposit on the air cathode having negative oxygen ion.And the porous carbon air cathode used at present is all piled up pore-creating with material with carbon element and obtained, the utilance in duct is low, poor connectivity and mass transfer ability, makes discharging product Li
2o
2limited storage space, directly cause the overpotential of lithium-air battery high, discharge and recharge utilize rate variance and cycle-index few.On the other hand, the load of hydrogen reduction in existing porous carbon air cathode/precipitation catalyst mainly still adopts the mode of mechanical mixture, effectively can not play the cooperative effect between carrier and catalyst, be degrading lithium-air battery energy conversion efficiency and high rate performance further.
Summary of the invention
The present invention will solve the technical problem that lithium-air battery overpotential in prior art is high, discharge and recharge utilizes rate variance and cycle-index is few, a kind of multi-stage artery structure is provided, catalyst is modified at absolute construction on electrode, lithium-air battery 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 multi-stage artery structure, the hollow carbon sphere@carbon paper air electrode material that nanocrystalline catalyst is modified, nanocrystalline catalyst is attached on the inwall of hollow carbon sphere, and 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 μm.
In technique scheme, the wall thickness of the hollow carbon sphere of described air electrode material is 3 ~ 30nm.
In technique scheme, in described air electrode material, the load capacity of nanocrystalline catalyst is 5 ~ 40%.
A preparation method for lithium-air battery air electrode, this preparation method mainly comprises the following steps:
(1) adopt
legal system is for high dispersive silicon ball;
(2) by sulfhydrylization reagent and above-mentioned silicon ball, sulfydryl SiClx ball after back flow reaction, is obtained;
(3) by sulfydryl SiClx ball electrophoresis in the network space of carbon paper, obtain sulfydryl SiClx ball carbon paper electrode;
(4) above-mentioned sulfydryl SiClx ball carbon paper electrode is immersed in the precursor salt solution of noble metal or transition metal oxide, filter, dry, under the protection of argon hydrogen mixed atmosphere, in the temperature lower calcination 1 ~ 3 hour of 200 ~ 350 DEG C, obtain nanocrystalline catalyst-silicon ball@carbon paper compound;
(5) above-mentioned nanocrystalline catalyst-silicon ball carbon paper compound is infiltrated 10 ~ 30% containing in carbon solution; filter; dry; under nitrogen protection; in the temperature lower calcination 1 ~ 3 hour of 800 ~ 850 DEG C; obtain multi-stage artery structure, the hollow carbon sphere@carbon paper air electrode that nanocrystalline catalyst is modified.
Wherein, described in step (5) is sucrose, glucose, phenolic resins, furfuryl alcohol, styrene or cyclodextrin solution containing carbon solution.
In technique scheme, the precursor salt solution of described noble metal is the acetylacetone,2,4-pentanedione solution of palladium, platinum or gold; The precursor salt solution of described transition metal oxide is 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: concentrated ammonia liquor, ethanol, deionized water and tetraethoxysilane are joined successively in round-bottomed flask, stir 5 ~ 18 hours, the product obtained is centrifuged separation, washs and drying under 100 DEG C of conditions, obtains high dispersive silicon ball.
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 successively in toluene, 110 DEG C backflow 10 ~ 20 hours, then room temperature cooling, centrifugal, washing, dry, obtain sulfydryl SiClx ball.
In technique scheme, described sulfhydrylization reagent is mercaptoethanol, 3-mercaptopropyi trimethoxy silane 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 sulfydryl SiClx ball is scattered in acetone and methanol mixed solvent, electrophoretic voltage is 15 ~ 25V, obtains sulfydryl SiClx ball carbon paper electrode.
In technique scheme, described acetone and the volume ratio of methyl alcohol are 1:(0.1-10).
In technique scheme, in the argon hydrogen gaseous mixture described in step (4), hydrogen and argon content are respectively 5% and 95%.
A kind of lithium-air battery air electrode of the present invention and preparation method thereof has following beneficial effect:
1, a kind of lithium-air battery air electrode provided by the invention is the hollow carbon sphere@carbon paper integrated electrode that the nanocrystalline catalyst with multi-stage artery structure is modified, and is the absolute construction that nanocrystalline catalyst is modified at the inwall of hollow carbon sphere.Nanocrystalline catalyst and the micropore of air electrode of the present invention provide catalytic site; Intercommunicating pore between spherical shell provides the transmission channel of oxygen and electrolyte; Macropore (empty spherical shell) provides solid discharge product Li
2o
2the place depositing/deviate from.Be the FESEM figure of the hollow carbon sphere@carbon paper air electrode of palladium modification prepared by the embodiment of the present invention one as Fig. 1.This figure can illustrate that air electrode material of the present invention has multi-stage artery structure.Fig. 2 is N2 adsorption curve and the graph of pore diameter distribution of the hollow carbon sphere@carbon paper air electrode of palladium modification prepared by the embodiment of the present invention one.This figure can illustrate that air electrode material of the present invention has the multi-stage artery structures such as micropore, mesoporous and macropore.
2, preparation method's reasonable combination hard template method and the electrophoretic techniques of lithium-air battery air electrode provided by the invention; its technique is simple, easy to operate, cost is low, easily accomplish scale production; and do not need to add binding agent; eliminate complicated powder electrode preparation process, significantly improve the stability of air cathode.When the air electrode prepared of the method is for lithium-air battery, effectively can improve the specific energy of lithium-air battery, energy utilization efficiency, high rate performance and cyclical stability etc.Wherein, comparatively business carbon air electrode improves 37 times to high rate performance, cyclical stability improves 5 times, overpotential brings up to 77% by 60%, and especially cycle life is significantly increased to 205 times the longest 100 times from current bibliographical information.Fig. 3 is the charging and discharging curve of hollow carbon sphere@carbon paper air electrode for lithium-air battery of palladium modification prepared by the embodiment of the present invention one, and limit capacity is 1000mAh g
-1, current density is 300mA g
-1.This figure can illustrate that the lithium-air battery cycle performance including air electrode of the present invention reaches 205 times, is 2 times of 100 times best in the world circulations of report at present.Fig. 4 is the cycle performance curve of hollow carbon sphere@carbon paper air electrode for lithium-air battery of palladium modification prepared by the present embodiment one, and limit capacity is 1000mAh g
-1, current density is 300mA g
-1.This figure can illustrate that the discharge voltage of the lithium-air battery including air electrode of the present invention does not significantly reduce along with the increase of cycle-index.
Accompanying drawing explanation
Fig. 1 is the FESEM figure of the hollow carbon sphere@carbon paper air electrode of palladium modification prepared by the embodiment of the present invention one.
Fig. 2 is N2 adsorption curve and the graph of pore diameter distribution of the hollow carbon sphere@carbon paper air electrode of palladium modification prepared by the embodiment of the present invention one.
Fig. 3 is the charging and discharging curve of hollow carbon sphere@carbon paper air electrode for lithium-air battery of palladium modification prepared by the embodiment of the present invention one, and limit capacity is 1000mAh g
-1, current density is 300mA g
-1.
Fig. 4 is the cycle performance curve of hollow carbon sphere@carbon paper air electrode for lithium-air battery of palladium modification prepared by the embodiment of the present invention one, 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 is the hollow carbon sphere@carbon paper electrode material that the nanocrystalline catalyst of multi-stage artery structure is modified, and nanocrystalline catalyst is attached on the inwall of hollow carbon sphere, and its load capacity is 5 ~ 40%; Hollow carbon sphere is present in the network space of carbon paper, and spherical shell internal diameter is 0.1 ~ 10 μm, and the wall thickness of hollow carbon sphere is 3 ~ 30nm.Wherein, nanocrystalline catalyst is noble metal or transition metal oxide.If noble metal can be palladium, platinum or gold; 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) adopt
legal system is for high dispersive silicon ball
Concentrated ammonia liquor, ethanol, deionized water and tetraethoxysilane are joined successively in round-bottomed flask, stir 5 ~ 18 hours, the product obtained is centrifuged separation, washs and drying under 100 DEG C of conditions, obtains high dispersive silicon ball.
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 toluene successively, 110 DEG C backflow 10 ~ 20 hours, then room temperature cooling, centrifugal, washing, dry, obtain sulfydryl SiClx ball.
Described sulfhydrylization reagent is mercaptoethanol, 3-mercaptopropyi trimethoxy silane or mercaptopropionic acid.
(3) by sulfydryl SiClx 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 sulfydryl SiClx ball is scattered in acetone and methanol mixed solvent, and electrophoretic voltage is 15 ~ 25V, obtains sulfydryl SiClx ball carbon paper electrode.
Described acetone and the volume ratio of methyl alcohol are 1:(0.1-10).
(4) above-mentioned sulfydryl SiClx ball carbon paper electrode is immersed in the precursor salt solution of noble metal or transition metal oxide, filter, dry, under argon hydrogen mixed atmosphere (hydrogen 5%) protection, in the temperature lower calcination 1 ~ 3 hour of 200 ~ 350 DEG C, obtain nanocrystalline catalyst-silicon ball@carbon paper compound;
The precursor salt solution of described noble metal is the acetylacetone,2,4-pentanedione solution of palladium, platinum or gold; The precursor salt solution of described transition metal oxide is nitrate or the acetate of manganese dioxide, cobaltosic oxide or di-iron trioxide.
(5) above-mentioned nanocrystalline catalyst-silicon ball carbon paper compound is infiltrated 10 ~ 30% containing in carbon solution; filter, dry, under nitrogen protection; in the temperature lower calcination 1 ~ 3 hour of 800 ~ 850 DEG C, obtain the hollow carbon sphere@carbon paper air electrode that nanocrystalline catalyst is modified.
Wherein, described in step (5) is sucrose, glucose, phenolic resins, furfuryl alcohol, styrene or cyclodextrin solution containing carbon solution.
Embodiment one
(1) 15mL concentrated ammonia liquor, 150mL ethanol and 15mL deionized water, 15mL tetraethoxysilane are joined successively in round-bottomed flask and stirred 5 hours, the product obtained is centrifuged separation, washs and drying under 100 DEG C of conditions, obtains high dispersive silicon ball.
(2) 6mL3-mercaptopropyi trimethoxy silane and 2.0g silicon ball join in 200mL toluene successively, 110 DEG C backflow 10 hours, then room temperature cooling, centrifugal, washing, dry, obtain sulfydryl SiClx ball.
(3) two electrodes are respectively carbon paper and steel disc, and electrode spacing is 0.5cm, and electrolyte is that sulfydryl SiClx ball is scattered in the acetone and methanol mixed solvent that volume ratio is 1:1, and electrophoretic voltage is 15V, obtains sulfydryl SiClx ball carbon paper electrode.
(4) sulfydryl SiClx ball carbon paper electrode being immersed in mass concentration is half an hour in the chloroformic solution of the palladium acetylacetonate of 5%; filter, dry; protect lower 300 DEG C of calcinings 1 hour at argon hydrogen mixed atmosphere (hydrogen 5%), obtain palladium-silicon ball@carbon paper compound.
(5) palladium-silicon ball@carbon paper compound is infiltrated half an hour in the sucrose solution of 10%, filtration, drying, under nitrogen protection 850 DEG C calcining 3 hours, 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 of palladium modification prepared by the present embodiment one.As seen from the figure, this air electrode material has multi-stage artery structure, and empty spherical shell provides lithium peroxide memory space, intercommunicating pore provides electrolyte and the transmission channel of oxygen, catalyst to be to regulate the depositing behavior of discharging product.
Fig. 2 is N2 adsorption curve and the graph of pore diameter distribution of the hollow carbon sphere@carbon paper air electrode of palladium modification prepared by the present embodiment one.As seen from the figure, this air electrode material has the multi-stage artery structures such as micropore, mesoporous and macropore.
Fig. 3 is the charging and discharging curve of hollow carbon sphere@carbon paper air electrode for lithium-air battery of palladium modification prepared by the present embodiment one, and limit capacity is 1000mAh g
-1, current density is 300mA g
-1.As seen from the figure, the lithium-air battery cycle performance including the present embodiment air electrode reaches 205 times, is 2 times of 100 times best in the world circulations of report at present.
Fig. 4 is the cycle performance curve of hollow carbon sphere@carbon paper air electrode for lithium-air battery of palladium modification prepared by the present embodiment one, and limit capacity is 1000mAh g
-1, current density is 300mA g
-1.As seen from the figure, the discharge voltage including the lithium-air battery of the present embodiment air electrode does not significantly reduce along with the increase of cycle-index.
Embodiment two
(1) 15mL concentrated ammonia liquor, 300mL ethanol and 75mL deionized water, 30mL tetraethoxysilane are joined successively in round-bottomed flask and stirred 10 hours, the product obtained is centrifuged separation, washs and drying under 100 DEG C of conditions, obtains high dispersive silicon ball.
(2) 30mL mercaptopropionic acid and 2.0g silicon ball join in 200mL toluene successively, 110 DEG C backflow 12 hours, then room temperature cooling, centrifugal, washing, dry, obtain sulfydryl SiClx ball.
(3) two electrodes are respectively carbon paper and steel disc, and electrode spacing is 2.0cm, and electrolyte is that sulfydryl SiClx ball is scattered in the acetone and methanol mixed solvent that volume ratio is 10:1, and electrophoretic voltage is 25V, obtains sulfydryl SiClx ball carbon paper electrode.
(4) sulfydryl SiClx ball carbon paper electrode being immersed in mass concentration is half an hour in the chlorauric acid solution of 20%; filter, dry; protect lower 200 DEG C of calcinings 3 hours at argon hydrogen mixed atmosphere (hydrogen 5%), obtain gold-hollow silicon ball@carbon paper compound.
(5) gold-silicon ball@carbon paper compound is infiltrated half an hour in the glucose solution of 15%, filtration, drying, under nitrogen protection 800 DEG C calcining 3 hours, 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 round-bottomed flask and stirred 18 hours, the product obtained is centrifuged separation, washs and drying under 100 DEG C of conditions.
(2) 20mL mercaptoethanol and 2.0g silicon ball join in 200mL toluene successively, 110 DEG C backflow 15 hours, then room temperature cooling, centrifugal, washing, dry, obtain sulfydryl SiClx ball.
(3) two electrodes are respectively carbon paper and steel disc, and electrode spacing is 1.0cm, and electrolyte is that sulfydryl SiClx ball is scattered in the acetone and methanol mixed solvent that volume ratio is 1:10, and electrophoretic voltage is 20V, obtains sulfydryl SiClx ball carbon paper electrode.
(4) sulfydryl SiClx ball carbon paper electrode being immersed in mass concentration is half an hour in the manganese acetate solution of 8%; filter, dry; protect lower 350 DEG C of calcinings 3 hours at argon hydrogen mixed atmosphere (hydrogen 5%), obtain manganese dioxide-silicon ball@carbon paper compound.
(5) manganese dioxide-silicon ball@carbon paper compound is infiltrated half an hour in the phenol resin solution of 30%, filtration, drying, under nitrogen protection 850 DEG C calcining 1 hour, 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 round-bottomed flask and stirred 18 hours, the product obtained is centrifuged separation, washs and drying under 100 DEG C of conditions.
(2) 15mL3-mercaptopropyi trimethoxy silane and 2.0g silicon ball join in 200mL toluene successively, 110 DEG C backflow 20 hours, then room temperature cooling, centrifugal, washing, dry, obtain sulfydryl SiClx ball.
(3) two electrodes are respectively carbon paper and steel disc, and electrode spacing is 1.5cm, and electrolyte is that sulfydryl SiClx ball is scattered in the acetone and methanol mixed solvent that volume ratio is 1:2, and electrophoretic voltage is 15V, obtains sulfydryl SiClx ball carbon paper electrode.
(4) sulfydryl SiClx ball carbon paper electrode being immersed in mass concentration is half an hour in the iron nitrate solution of 12%; filter, dry; protect lower 350 DEG C of calcinings after 1 hour at argon hydrogen mixed atmosphere (hydrogen 5%), obtain di-iron trioxide-silicon ball@carbon paper compound.
(5) di-iron trioxide-silicon ball@carbon paper compound is infiltrated half an hour in the furfuryl alcohol solution of 20%, filtration, drying, under nitrogen protection 850 DEG C calcining 1 hour, 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 round-bottomed flask and stirred 10 hours, the product obtained is centrifuged separation, washs and drying under 100 DEG C of conditions, obtains high dispersive silicon ball.
(2) 30mL3-mercaptopropyi trimethoxy silane and 2.0g silicon ball join in 200mL toluene successively, 110 DEG C backflow 12 hours, then room temperature cooling, centrifugal, washing, dry, obtain sulfydryl SiClx ball.
(3) two electrodes are respectively carbon paper and steel disc, and electrode spacing is 2.0cm, and electrolyte is that sulfydryl SiClx ball is scattered in the acetone and methanol mixed solvent that volume ratio is 10:1, and electrophoretic voltage is 25V, obtains sulfydryl SiClx ball carbon paper electrode.
(4) sulfydryl SiClx ball carbon paper electrode being immersed in mass concentration is half an hour in the acetylacetone,2,4-pentanedione platinum solution of 20%; filter, dry; protect lower 200 DEG C of calcinings 3 hours at argon hydrogen mixed atmosphere (hydrogen 5%), obtain platinum-silicon ball@carbon paper compound.
(5) platinum-silicon ball@carbon paper compound is infiltrated half an hour in the styrene solution of 15%, filtration, drying, under nitrogen protection 800 DEG C calcining 3 hours, 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 round-bottomed flask and stirred 18 hours, the product obtained is centrifuged separation, washs and drying under 100 DEG C of conditions, obtains high dispersive silicon ball.
(2) 15mL3-mercaptopropyi trimethoxy silane and 2.0g silicon ball join in 200mL toluene successively, 110 DEG C backflow 20 hours, then room temperature cooling, centrifugal, washing, dry, obtain sulfydryl SiClx ball.
(3) two electrodes are respectively carbon paper and steel disc, and electrode spacing is 1.5cm, and electrolyte is that sulfydryl SiClx ball is scattered in the acetone and methanol mixed solvent that volume ratio is 1:2, and electrophoretic voltage is 15V, obtains sulfydryl SiClx ball carbon paper electrode.
(4) sulfydryl SiClx ball carbon paper electrode being immersed in mass concentration is half an hour in the cobalt nitrate solution of 15%; filter, dry; protect lower 350 DEG C of calcinings 1 hour at argon hydrogen mixed atmosphere (hydrogen 5%), obtain cobaltosic oxide-silicon ball@carbon paper compound.
(5) cobaltosic oxide-silicon ball@carbon paper compound is infiltrated half an hour in the cyclodextrin solution of 20%, filtration, drying, under nitrogen protection 850 DEG C calcining 1 hour, obtain the hollow carbon sphere@carbon paper air electrode that cobaltosic oxide is modified.
Obviously, above-described embodiment is only for clearly example being described, and the restriction not 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 exhaustive without the need to also giving all execution modes.And thus the apparent change of extending out or variation be still among the protection range of the invention.
Claims (14)
1. a lithium-air battery air electrode, it is characterized in that, this air electrode is multi-stage artery structure, the hollow carbon sphere@carbon paper air electrode material that nanocrystalline catalyst is modified, nanocrystalline catalyst is attached on the inwall of hollow carbon sphere, and 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 μm.
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, in described air electrode material, the load capacity of nanocrystalline catalyst is 5 ~ 40%.
6. the preparation method of lithium-air battery air electrode according to claim 1, is characterized in that, this preparation method mainly comprises the following steps:
(1) adopt
legal system is for high dispersive silicon ball;
(2) by sulfhydrylization reagent and above-mentioned silicon ball, sulfydryl SiClx ball after back flow reaction, is obtained;
(3) by sulfydryl SiClx ball electrophoresis in the network space of carbon paper, obtain sulfydryl SiClx ball carbon paper electrode;
(4) above-mentioned sulfydryl SiClx ball carbon paper electrode is immersed in the precursor salt solution of noble metal or transition metal oxide, filter, dry, under the protection of argon hydrogen mixed atmosphere, in the temperature lower calcination 1 ~ 3 hour of 200 ~ 350 DEG C, obtain nanocrystalline catalyst-silicon ball@carbon paper compound;
(5) above-mentioned nanocrystalline catalyst-silicon ball carbon paper compound is infiltrated 10 ~ 30% containing in carbon solution, filter, dry, under nitrogen protection, in the temperature lower calcination 1 ~ 3 hour of 800 ~ 850 DEG C, obtain multi-stage artery structure, the hollow carbon sphere@carbon paper air electrode that nanocrystalline catalyst is modified;
Wherein, described in step (5) is sucrose, glucose, phenolic resins, furfuryl alcohol, styrene or cyclodextrin solution containing carbon solution.
7. preparation method according to claim 6, is characterized in that, the precursor salt solution of described noble metal is the acetylacetone,2,4-pentanedione solution of palladium, platinum or gold; The precursor salt solution of described transition metal oxide is 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: concentrated ammonia liquor, ethanol, deionized water and tetraethoxysilane are joined successively in round-bottomed flask, stir 5 ~ 18 hours, the product obtained is centrifuged separation, washs and drying under 100 DEG C of conditions, obtains high dispersive silicon ball.
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 successively in toluene, and 110 DEG C are refluxed 10 ~ 20 hours, then room temperature cooling, centrifugal, washing, dry, obtain sulfydryl SiClx ball.
11. preparation methods according to claim 10, is characterized in that, described sulfhydrylization reagent is mercaptoethanol, 3-mercaptopropyi trimethoxy silane or mercaptopropionic acid.
12. preparation methods 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 sulfydryl SiClx ball is scattered in acetone and methanol mixed solvent, electrophoretic voltage is 15 ~ 25V, obtains sulfydryl SiClx ball carbon paper electrode.
13. preparation methods according to claim 12, is characterized in that, described acetone and the volume ratio of methyl alcohol are 1:(0.1-10).
14. preparation methods according to claim 6, is characterized in that, in the argon hydrogen gaseous mixture described in step (4), hydrogen and argon content are respectively 5% and 95%.
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| JP2015053136A (en) * | 2013-09-05 | 2015-03-19 | スズキ株式会社 | Lithium air battery and positive complex |
| 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 |
| 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 |
| 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 |
| EP3989312A4 (en) * | 2019-06-21 | 2023-08-02 | Shanghai Institute of Ceramics, Chinese Academy of Sciences | A class of porous metal oxide based electrochemical energy storage materials, preparation method therefor and use thereof |
| 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 |
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| JP5104942B2 (en) * | 2008-11-27 | 2012-12-19 | トヨタ自動車株式会社 | Air secondary battery |
| CN105375039B (en) * | 2010-08-31 | 2018-06-22 | 中国科学院上海硅酸盐研究所 | A kind of 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 |
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