CN104709895A - Electrode material with multistage aperture distribution structure and preparation and application thereof - Google Patents
Electrode material with multistage aperture distribution structure and preparation and application thereof Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention relates to an electrode material with a multistage aperture distribution structure and preparation and application thereof, the electrode material comprises basic structural units which are connected through carbon skeleton, the carbon skeleton is prepared by carbonization of a carbon-containing organic matter as a binder, the electrode material particle diameter is 0.2-20um, and the basic structure unit includes a granule material, a one-dimensional linear material and a graphene sheet material. In the electrode material, smaller size pores are built by gaps among the structural units, and larger size pores are built by larger gaps among larger size electrode material particles, so that the target of double pore size distribution of the material can be realized, and the function of the electrode material in the battery application can be greatly expanded. The electrode material is used in lithium-air batteries, lithium-sulfur batteries and lithium thionyl chloride battery positive electrodes, reactant mass transfer in electrodes can be effectively improved, and the battery charge discharge capacity can be improved.
Description
Technical field
The invention belongs to electrode materials field, be specifically related to a kind of to there is electrode materials of Novel hole structure and preparation method thereof, and its application in the battery.
Background technology
Along with developing rapidly of electronics, signal equipment and power truck, people propose requirements at the higher level to battery performance.Conventional lithium ion battery entered the development of two more than ten years, and its energy density is more than 200Wh/kg at present, but this still can not meet the requirement of association area, but was limited by the specific storage of electrode active material, and its energy density is close to ultimate value.For research that is once various or secondary high energy density cells, become the research and development emphasis of whole academia and industrial community.
Such as, lithium-sulfur cell is a kind of is negative pole with metallic lithium, and sulphur is the secondary cell of positive active material.Metallic lithium as negative material has minimum theoretical voltage, its theoretical specific capacity up to 3,862mAh/g, and as the sulphur specific storage of positive active material also up to 1,672mAh/g.Therefore, lithium-sulfur cell has high specific energy.Take lithium as standard, its theoretical value can reach 2,600Wh/kg, and actual specific energy is also far above lithium ion battery, and the maximum of current International reporting can reach 420Wh/kg, has application prospect in civilian and military domain.Identical with lithium-sulfur cell, lithium-air battery negative pole adopts metallic lithium equally, is oxygen unlike its positive active material, and directly can obtain by air, thus have higher energy density, theoretical value can reach 11,000Wh/kg.
In numerous electrode materials, carbon material has higher specific conductivity, pore volume, the many merits such as specific surface area, and its concrete physical parameter has important impact for battery performance.For example, during for lithium-sulfur cell, mix with active substance sulphur, in order to overcome the lower shortcoming of its specific conductivity, improve its utilization ratio; Meanwhile, the duct of carbon material, for fixing active substance, suppresses its shuttling back and forth in electrode to have vital role, is conducive to the cyclical stability improving battery.During for lithium-air battery, carbon material duct is the depositional site of battery discharge product lithium peroxide, therefore, is the important parameter determining discharge capacity of the cell.
The pore property of carbon material is determined by himself concrete appearance structure.Such as, conventional granule type carbon material, its hole forms primarily of two portions, and one is the sunk structure of particle surface, and this part mainly forms micropore; Two is ducts that intergranular space builds, and its concrete pore size distribution depends primarily on the size of carbon granule self, and Main Function is played in this part duct.Usually, the pore size distribution of carbon material is relatively single, and its aperture concentrates on a certain region, and particle is comparatively large, and aperture is just comparatively large, otherwise, just less.Consider different function needs, in practical application, the requirement of electrode reaction to electrode materials aperture is diversification, and this constructional feature of carbon material certainly will limit the maximum performance of its effect.
Such as, as lithium-air battery, the deposition of discharging product requires that electrode materials duct mainly concentrates on mesoporous region, to obtain maximum duct space availability ratio; On the other hand, the transmission of reactant oxygen in whole electrode needs passing hole channel to carry out equally, mesoporous very easily blocked, therefore hinders gas transfer, at this moment just needs the duct with larger aperture.Due to the unicity of carbon material pore structure, in order to address this problem, the method that researchist adopts usually is supported by carbon material on the propping material with larger aperture hole, such as, and the carbon paper built by carbon fiber, foamed metal etc.From effect, the program is very big facilitates the duct utilization ratio of carbon material self, but due to the introducing of propping material, the actual specific capacity of electrode materials does not obtain substantive raising.How by structure design, being built the pore size distribution of diversification by carbon material self, is address this problem basic.
Summary of the invention
The object of the present invention is to provide a kind of electrode materials with multi-stage porous distributed architecture.
In order to achieve the above object, the technical solution used in the present invention is as follows:
Electrode materials is connected and composed by skeleton carbon by basic structural unit, and skeleton carbon is prepared from by the carbonaceous organic material carbonization as binding agent; Electrode materials particle diameter is 0.2 ~ 20um;
Wherein, preparation process is formed in 500 ~ 1200 celsius temperature carbonizations with after the carbonaceous organic material of binding agent mixes by basic structural unit raw material, and in preparation process, the mass ratio of basic structural unit raw material and binding agent is 1:5 ~ 20:1; Basic structural unit is one or two or more kinds in particle type materials, one dimension filamentary material, graphene film layer material, wherein granule type basic structural unit particle diameter is 2 ~ 200nm, one dimension wire type basic structural unit diameter is 5 ~ 200nm, and length is 0.2 ~ 10um;
Basic structural unit comprises carbon material, metal or metal oxide.
Described carbon material comprises one or two or more kinds in KB300, KB600, Super P, the BP2000 of particle, acetylene black, graphite, the single wall of one dimension or multi-walled carbon nano-tubes, one or two or more kinds in hollow carbon pipe, carbon fiber, carbon cloth, and graphene sheet layer carbon material;
Metallic element in described metal or metal oxide is one or two or more kinds of Fe, Co, Ni, Cu, Ag, Pt, Pd, Au, Ir, Ru, Nb, Y, Rh, Cr, Zr, Ce, Ti, Mo, Mn, Zn, W, Sn, La and V.
The preparation method of described electrode materials, detailed process is as follows:
Wherein, described skeleton carbon is prepared by carbonaceous organic material carbonization, and detailed process is as follows:
Described basic structural unit is scattered in obtained suspension liquid in solvent, concentration is 1 ~ 100mg/ml solvent, and preferable range is 10 ~ 100mg/ml solvent; Described solvent is, water, ethanol, Virahol, ethylene glycol, polyvinylpyrrolidone, DMSO, DMF, methylene dichloride, dithiocarbonic anhydride, dioxane, tetrahydrofuran (THF), benzene, one or more in chloroform;
In suspension liquid, add the carbonaceous organic material as binding agent, it is 1:20 ~ 5:1 with the ratio of the raw materials quality as basic structural unit, and preferable range is 1:5 ~ 2:1; Described carbonaceous organic material comprises, sucrose, resol, melmac, polyacrylonitrile, polypropylene, polyethylene, one or two or more kinds in gelatin;
Said mixture is stirred 1 ~ 5 hour, mixes; Stir in 60 ~ 100 degrees Celsius of oil baths, solvent flashing, proceed to vacuum drying oven further, 60 degrees Celsius of oven dry; Using said mixture as precursor, under inert atmosphere, 500 ~ 1200 degree of carbonizations 1 ~ 5 hour, Temperature fall, to room temperature, obtains described electrode materials.
Described rare gas element is nitrogen, the one in argon gas.
Electrode materials of the present invention can be directly used in prepares lithium-air battery positive pole, is used for product deposition with material internal duct, and intergranular pores road is used for oxygen transmission.
Electrode materials of the present invention also can be used for the preparation of Lithium-sulphur battery anode material, adopts known method, utilizes the liquefaction of sulphur under high temperature to realize its deposition in material duct, and then for the preparation of positive pole.
Carbon material of the present invention also can be used for lithium thionyl chloride cell, is used for product deposition with material internal duct, and intergranular pores road is used for ion transport.
The application of electrode materials in lithium-sulfur cell, itself and elemental sulfur compound are used as positive electrode material, and wherein the massfraction of sulphur is 50 ~ 85%.
Tool of the present invention has the following advantages:
1. in order to realize the multi-stage porous distribution of material, the present invention sets about from the structure composition design of material, this principle of gap length between particle is determined according to grain diameter size, using selected material as structural unit, carbonaceous organic material is utilized to connect combination as binding agent, build the carbon material with greater particle size, i.e. " secondary granulation ".Secondary granulation carbon material is inner, smaller aperture due hole is built by the gap between carbon unit, and the interparticle comparatively wide arc gap of the secondary granulation of greater particle size builds larger aperture hole, thus achieve the target of a kind of material Based on Dual-Aperture distribution, greatly expand the function that it possesses in battery applications.On the other hand, as the carbonaceous material of binding agent after carbonization, while playing skeletal support effect, himself also has vesicular structure, thus the extreme enrichment pore property of prepared material.
2. material raw materials enriches, and can extensively adopt existing commercialization material as structural unit.
3. material preparation process is simple, and without the need to template, without the introducing of other impurity, therefore without the need to aftertreatment, greatly simplify technical process, cost is low.
4., by structure design, realize a kind of Based on Dual-Aperture distribution of material, material is possessed difunctional, and be independent of each other each other.
Accompanying drawing explanation
Fig. 1. the pore passage structure that traditional electrode materials builds;
Fig. 2. adopt the pore passage structure that electrode materials of the present invention builds;
Fig. 3. adopt electrode materials prepared by the method for the invention, the electrode appearance structure of preparation.
Embodiment
Embodiment 1
100mg KB600 is scattered in 10ml water, then adds sucrose 100mg wherein, fully stir, after mixing, stir in 70 degrees Celsius of oil baths, solvent flashing, proceed to vacuum drying oven further, 60 degrees Celsius of oven dry.
Using said mixture as precursor, under argon gas atmosphere, 900 degree of carbonizations 4 hours, Temperature fall, to room temperature, obtains described carbon material.
Using above-mentioned carbon material as electrode materials, itself and ptfe emulsion (PTFE, massfraction is 5%) is blended in ethanol, obtain electrode slurry, wherein the mass ratio of carbon dust and tetrafluoroethylene is 4:1, and solid matter and solvent ratios are 20mg solid/ml solvent; Adopt the mode of roll-in, prepare sheet-like carbon layer, in 60 degrees Celsius of oven dry, in carbon-coating, carbon material area density is 3mg/cm
2.
Using the LiTFSI/TEGDME of 1M as electrolytic solution, by lithium anode, porous carbon layer, porous polypropylene barrier film, positive pole is fitted successively, assembling lithium-air monocell.In 1.2 atmospheric pure oxygen atmospheres, adopt 80mA/g(with carbon material quality for standard) current density discharge, stopping potential is 2V, and loading capacity is 2.6 times of simple KB600 carbon dust.
Embodiment 2
100mg KB300 is scattered in 10ml Virahol, then adds resol 400mg wherein, fully stir, after mixing, stir in 70 degrees Celsius of oil baths, solvent flashing, proceed to vacuum drying oven further, 60 degrees Celsius of oven dry.
Using said mixture as precursor, under argon gas atmosphere, 900 degree of carbonizations 4 hours, Temperature fall, to room temperature, obtains described carbon material.
Using above-mentioned carbon material as electrode materials, itself and ptfe emulsion (PTFE, massfraction is 5%) is blended in ethanol, obtain electrode slurry, wherein the mass ratio of carbon dust and tetrafluoroethylene is 4:1, and solid matter and solvent ratios are 20mg solid/ml solvent; Adopt the mode of roll-in, prepare sheet-like carbon layer, in 60 degrees Celsius of oven dry, in carbon-coating, carbon material area density is 6mg/cm
2.
With the LiAlCl of 1M
4/ SOCl
2for electrolytic solution, porous polypropylene is as barrier film, and metallic lithium, as negative pole, is evaluated prepared carbon positive pole.Result shows, the carbon positive pole 5mA/cm prepared by the present invention
2under, improve 50% compared to KB300 capacity.
Embodiment 3
100mg BP2000 is scattered in 10ml water, then adds gelatin 200mg wherein, fully stir, after mixing, stir in 70 degrees Celsius of oil baths, solvent flashing, proceed to vacuum drying oven further, 60 degrees Celsius of oven dry.
Using said mixture as precursor, under argon gas atmosphere, 1000 degree of carbonizations 4 hours, Temperature fall, to room temperature, obtains described carbon material.
Mixed with mass ratio 3:1 ball milling in ball grinder with above-mentioned carbon material by sulphur, then, in the tube furnace of argon shield, 155 degrees Celsius keep 2 hours, elemental sulfur liquefied and enters in the duct of carbon dust structure, obtaining carbon sulphur combination electrode material.Further, using it as positive electrode material, PTFE is as binding agent, and the two mass ratio is 9:1, and solid matter and solvent ratios are 20mg solid/ml solvent; Adopt the mode of roll-in, prepare pellet electrode, in 60 degrees Celsius of oven dry, prepare lithium-sulfur cell positive pole, wherein, the area density of active substance sulphur is 3mg/cm
2.
Using the LiTFSI/DOL:DME(solvent quality of 1M ratio for 1:1) as electrolytic solution, by lithium anode, porous polypropylene barrier film, carbon-sulfur compound positive pole is fitted successively, assembling button cell.Adopt 0.1C constant current charge-discharge, evaluate.Result shows, compared to the battery structure without porous functional layer, and scheme of the present invention, circulating battery 50 times, capability retention increase about 40%.
Embodiment 4
By 100mg MnO
2be scattered in 10ml DMSO, then add polyacrylonitrile 100mg wherein, fully stir, after mixing, stir in 70 degrees Celsius of oil baths, solvent flashing, proceed to vacuum drying oven further, 60 degrees Celsius of oven dry.
Using said mixture as precursor, under argon gas atmosphere, 900 degree of carbonizations 4 hours, Temperature fall, to room temperature, obtains described carbon material.
The identical technique of embodiment 1 is adopted to prepare lithium-air battery positive pole, wherein MnO
2area density be 2mg/cm
2.
Using the LiTFSI/TEGDME of 1M as electrolytic solution, by lithium anode, porous carbon layer, porous polypropylene barrier film, positive pole is fitted successively, assembling lithium-air monocell.In 1.2 atmospheric pure oxygen atmospheres, adopt 80mA/g(with Manganse Dioxide quality for standard) current density discharge, stopping potential is 2V, and loading capacity is simple MnO
22.3 times.
Embodiment 5
100mg acetylene black is scattered in 10ml Virahol, then adds melmac 80mg wherein, fully stir, after mixing, stir in 70 degrees Celsius of oil baths, solvent flashing, proceed to vacuum drying oven further, 60 degrees Celsius of oven dry.
Using said mixture as precursor, under argon gas atmosphere, 900 degree of carbonizations 3 hours, Temperature fall, to room temperature, obtains described carbon material.
Adopt the identical technique of embodiment 2 to prepare lithium-thionyl chloride battery positive pole, wherein carbon material area density is 6mg/cm
2.
With the LiAlCl of 1M
4/ SOCl
2for electrolytic solution, porous polypropylene is as barrier film, and metallic lithium, as negative pole, is evaluated prepared carbon positive pole.Result shows, the carbon positive pole 5mA/cm prepared by the present invention
2under, compared to acetylene black, capacity improves 60%.
Embodiment 6
100mg XC-72 is scattered in 10ml water, then adds sucrose 70mg wherein, fully stir, after mixing, stir in 70 degrees Celsius of oil baths, solvent flashing, proceed to vacuum drying oven further, 60 degrees Celsius of oven dry.
Using said mixture as precursor, under argon gas atmosphere, 1000 degree of carbonizations 4 hours, Temperature fall, to room temperature, obtains described carbon material.
Adopt the identical technique of embodiment 3 to prepare lithium-sulfur cell positive pole, wherein, sulphur load amount is 3mg/cm
2.
Using the LiTFSI/DOL:DME(solvent quality of 1M ratio for 1:1) as electrolytic solution, by lithium anode, porous polypropylene barrier film, carbon-sulfur compound positive pole is fitted successively, assembling button cell.Adopt 0.1C constant current charge-discharge, evaluate.Result shows, compared to the battery structure without porous functional layer, and scheme of the present invention, circulating battery 50 times, capability retention increase about 35%.
Embodiment 7
100mg Pd is scattered in 10ml water, then adds sucrose 50mg wherein, fully stir, after mixing, stir in 70 degrees Celsius of oil baths, solvent flashing, proceed to vacuum drying oven further, 60 degrees Celsius of oven dry.
Using said mixture as precursor, under argon gas atmosphere, 900 degree of carbonizations 4 hours, Temperature fall, to room temperature, obtains described carbon material.
Adopt the identical technique of embodiment 1 to prepare lithium-air battery positive pole, wherein the area density of metallic substance is 1mg/cm
2.
Using the LiTFSI/TEGDME of 1M as electrolytic solution, by lithium anode, porous carbon layer, porous polypropylene barrier film, positive pole is fitted successively, assembling lithium-air monocell.In 1.2 atmospheric pure oxygen atmospheres, adopt 80mA/g(with Pd quality for standard) current density discharge, stopping potential is 2V, and loading capacity is 4 times of simple Pd.
Embodiment 8
By 100mg graphene dispersion in 10ml water, then add sucrose 60mg wherein, fully stir, after mixing, stir in 70 degrees Celsius of oil baths, solvent flashing, proceed to vacuum drying oven further, 60 degrees Celsius of oven dry.
Using said mixture as precursor, under argon gas atmosphere, 1000 degree of carbonizations 4 hours, Temperature fall, to room temperature, obtains described carbon material.
Adopt the identical technique of embodiment 1 to prepare lithium-air battery positive pole, wherein the area density of carbon material is 3mg/cm
2.
Using the LiTFSI/TEGDME of 1M as electrolytic solution, by lithium anode, porous carbon layer, porous polypropylene barrier film, positive pole is fitted successively, assembling lithium-air monocell.In 1.2 atmospheric pure oxygen atmospheres, adopt 80mA/g(with carbon material quality for standard) current density discharge, stopping potential is 2V, and loading capacity is 2.5 times of simple Graphene.
Claims (8)
1. there is an electrode materials for multi-stage porous distributed architecture, it is characterized in that: electrode materials is connected and composed by skeleton carbon by basic structural unit, and skeleton carbon is prepared from by the carbonaceous organic material carbonization as binding agent; Electrode materials particle diameter is 0.2 ~ 20um;
Wherein, preparation process is formed in 500 ~ 1200 celsius temperature carbonizations with after the carbonaceous organic material of binding agent mixes by basic structural unit raw material, and in preparation process, the mass ratio of basic structural unit raw material and binding agent is 1:5 ~ 20:1; Basic structural unit is one or two or more kinds in particle type materials, one dimension filamentary material, graphene film layer material, wherein granule type basic structural unit particle diameter is 2 ~ 200nm, one dimension wire type basic structural unit diameter is 5 ~ 200nm, and length is 0.2 ~ 10um;
Basic structural unit comprises carbon material, metal or metal oxide.
2., according to electrode materials according to claim 1, it is characterized in that:
As basic structural unit, described carbon material comprises one or two or more kinds in KB300, KB600, Super P, the BP2000 of particle, acetylene black, graphite, the single wall of one dimension or multi-walled carbon nano-tubes, one or two or more kinds in hollow carbon pipe, carbon fiber, carbon cloth, and graphene sheet layer carbon material;
Metallic element in described metal or metal oxide is one or two or more kinds of Fe, Co, Ni, Cu, Ag, Pt, Pd, Au, Ir, Ru, Nb, Y, Rh, Cr, Zr, Ce, Ti, Mo, Mn, Zn, W, Sn, La and V.
3. a preparation method for electrode materials described in claim 1 or 2, wherein, described skeleton carbon is prepared by carbonaceous organic material carbonization, and detailed process is as follows:
Described basic structural unit is scattered in obtained suspension liquid in solvent, concentration is 1 ~ 100mg/ml solvent, and preferable range is 10 ~ 100mg/ml solvent;
In suspension liquid, add the carbonaceous organic material as binding agent, it is 1:20 ~ 5:1 with the ratio of the raw materials quality as basic structural unit, and preferable range is 1:5 ~ 2:1; Stir 1 ~ 5 hour, mix; Stir in 60 ~ 100 degrees Celsius of oil baths, solvent flashing, proceed to vacuum drying oven further, 60 degrees Celsius of oven dry;
Using said mixture as precursor, under inert atmosphere, 500 ~ 1200 degree of carbonizations 1 ~ 5 hour, Temperature fall, to room temperature, obtains described electrode materials.
4. according to preparation method according to claim 3, it is characterized in that: described solvent is one or two or more kinds in water, ethanol, Virahol, ethylene glycol, polyvinylpyrrolidone, DMSO, DMF, methylene dichloride, dithiocarbonic anhydride, dioxane, tetrahydrofuran (THF), benzene, chloroform.
5. according to preparation method according to claim 3, it is characterized in that: the described carbonaceous organic material as binding agent comprises one or two or more kinds in sucrose, resol, melmac, polyacrylonitrile, polypropylene, polyethylene, gelatin.
6. according to preparation method according to claim 3, it is characterized in that: described rare gas element is the one in nitrogen, argon gas.
7. an electrode materials according to claim 1 is as the application of positive electrode material in lithium-air battery or lithium thionyl chloride cell.
8. the application of electrode materials according to claim 1 in lithium-sulfur cell, itself and elemental sulfur compound are used as positive electrode material, and wherein the massfraction of sulphur is 50 ~ 85%.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105034498A (en) * | 2015-09-08 | 2015-11-11 | 无锡百灵传感技术有限公司 | Easily-cooled electric conduction substrate and preparation method thereof |
| CN105111702A (en) * | 2015-09-08 | 2015-12-02 | 无锡百灵传感技术有限公司 | Composite electrode material based on high-polymer material/graphene |
| CN107808955A (en) * | 2017-10-27 | 2018-03-16 | 湖南工业大学 | A kind of absorbent charcoal material with spherical structure and its preparation method and application |
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| CN109285990A (en) * | 2018-11-12 | 2019-01-29 | 武汉中原长江科技发展有限公司 | A kind of anode of lithium-thionyl chloride energy-type cells and preparation method thereof and lithium-thionyl chloride energy-type cells |
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| CN105034498A (en) * | 2015-09-08 | 2015-11-11 | 无锡百灵传感技术有限公司 | Easily-cooled electric conduction substrate and preparation method thereof |
| CN105111702A (en) * | 2015-09-08 | 2015-12-02 | 无锡百灵传感技术有限公司 | Composite electrode material based on high-polymer material/graphene |
| CN105034498B (en) * | 2015-09-08 | 2017-03-22 | 无锡百灵传感技术有限公司 | Easily-cooled electric conduction substrate and preparation method thereof |
| CN109509870A (en) * | 2017-09-15 | 2019-03-22 | 原子能和替代能源委员会 | Use Li2The method that S manufactures the electrode of lithium-sulfur cell as active material |
| CN109616619A (en) * | 2017-09-15 | 2019-04-12 | 原子能和替代能源委员会 | Prepare the method with the lithium-sulfur cell electrode of big active surface area |
| CN107808955A (en) * | 2017-10-27 | 2018-03-16 | 湖南工业大学 | A kind of absorbent charcoal material with spherical structure and its preparation method and application |
| CN107808955B (en) * | 2017-10-27 | 2021-09-10 | 湖南工业大学 | Activated carbon material with spherical structure and preparation method and application thereof |
| CN109205743A (en) * | 2018-11-02 | 2019-01-15 | 南京工业大学 | A kind of preparation method and applications of carbon nanotube composite titanium oxide porous carbon materials |
| CN109205743B (en) * | 2018-11-02 | 2021-04-13 | 南京工业大学 | Preparation method and application of carbon nanotube composite titanium oxide porous carbon material |
| CN109285990A (en) * | 2018-11-12 | 2019-01-29 | 武汉中原长江科技发展有限公司 | A kind of anode of lithium-thionyl chloride energy-type cells and preparation method thereof and lithium-thionyl chloride energy-type cells |
| CN109285990B (en) * | 2018-11-12 | 2021-11-16 | 武汉中原长江科技发展有限公司 | Positive electrode of lithium-thionyl chloride energy type battery, preparation method of positive electrode and lithium-thionyl chloride energy type battery |
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