CN107017404A - A kind of preparation method of nitrogen-doped carbon supported cobaltosic oxide electrode material - Google Patents

A kind of preparation method of nitrogen-doped carbon supported cobaltosic oxide electrode material Download PDF

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CN107017404A
CN107017404A CN201710440352.2A CN201710440352A CN107017404A CN 107017404 A CN107017404 A CN 107017404A CN 201710440352 A CN201710440352 A CN 201710440352A CN 107017404 A CN107017404 A CN 107017404A
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nitrogen
cobaltosic oxide
butyl
doped carbon
cobalt
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蒙延双
肖明军
朱福良
王功瑞
段超宇
杜梦奇
王琛
王磊
夏军
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Lanzhou University of Technology
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Lanzhou University of Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/46—Metal oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • Y02E60/10—Energy storage using batteries

Abstract

A kind of preparation method of nitrogen-doped carbon supported cobaltosic oxide electrode material, first uniformly mixes cobalt source with ionic liquid；It is then placed in tube furnace, 100 DEG C of 400 DEG C of 10 60min of insulation is warming up under an argon atmosphere, is further continued for being warming up to 600 DEG C of 1600 DEG C of 60 360min of insulation, is cooled to room temperature；It is warming up to 200 DEG C 700 DEG C in air atmosphere again, is incubated 20 120min, nitrogen-doped carbon supported cobaltosic oxide electrode material is obtained after cooling.Preparation process of the present invention is simple, and cobaltosic oxide particle is small, good dispersion, and the nitrogen content and cobaltosic oxide load capacity in carbon base body are adjustable.Because nitrogen-doped carbon matrix has good electric conductivity, and can effectively prevent bulk effect of the cobaltosic oxide particle in charge and discharge process, therefore the nitrogen-doped carbon supported cobaltosic oxide material prepared as lithium ion battery negative material when there is high lithium storage content and good cycle performance.

Description

A kind of preparation method of nitrogen-doped carbon supported cobaltosic oxide electrode material
Technical field
The present invention relates to the technology of preparing of electrode material, and in particular to nitrogen-doped carbon supported cobaltosic oxide electrode material Prepare, belong to energy and material and new material technology field.
Background technology
Metal oxide materials are rich with theoretical capacity height, reserves as a kind of new lithium ion battery negative material It is rich, with low cost, the advantages of chemical stability is high, but its electric conductivity is poor, causes the charge/discharge rates of such material relatively low, The enormousness expansion produced simultaneously in charge and discharge process and larger irreversible capacity first all limit such material Business application.In recent years, people attempt to prepare the metal oxide nano-material with specific morphology to attempt to reduce charge and discharge The Volume Changes of material in electric process.In addition researcher's trial prepares composite metal oxide electrode material, by not of the same race Oxide particle adulterates, and can improve the porosity of material, significantly improve wetting capacity of the electrolyte to electrode material, and improve electricity The stability of pole material, plays so-called cooperative effect.But the charge-discharge performance of such material and the improvement effect of cycle performance Fruit is still undesirable.Therefore researcher is attempted to prepare the metal oxide-loaded electrode material of various carbon, and carbon load can not only be carried The Volume Changes of material in charge and discharge process can also be played cushioning effect by the conductance of high electrode material.
Chinese patent CN101811696A discloses a kind of graphene-supported cobaltosic oxide nano composite material and its system Preparation Method.Take graphene oxide solution and divalent cobalt, high molecular surfactant mixing.Then with the alkali soluble for adding oxidant Stirring or ultrasonic 0.2 ~ 5 hour, is transferred in pyroreaction kettle after liquid mixing, is annealed 3 ~ 30 hours at 100 ~ 250 DEG C It is scrubbed, dry, produce graphene-supported cobaltosic oxide nano composite material to product.The size of cobaltosic oxide is controllable, The reduction of graphene oxide and the generation of cobaltosic oxide are completed simultaneously.
Chinese patent CN105513834A discloses a kind of bacteria cellulose graphene paper supported cobaltosic oxide flexible electrical The preparation method and application of pole material.Prepare bacteria cellulose slurry；Bacteria cellulose graphite paper is prepared, preparation contains cobalt salt Reaction solution, bacteria cellulose graphene paper is immersed in the reaction solution containing cobalt salt, and bacteria cellulose graphene paper is made and bears Cobaltosic oxide flexible electrode is carried, applied to ultracapacitor.The active material specific capacity is high, flexible electrode mechanical property is excellent Good, being prepared into ultracapacitor has good capacitive character.
Foregoing invention is modified using different-shape carbon base body to cobaltosic oxide material, but without reference to carbon base body Composition regulates and controls.
The content of the invention
The purpose of the present invention is that the electric conductivity of carbon material is improved by nitrogen atom doping, while providing the embedded work of lithium ion Property point, improve lithium storage content, cycle performance and high rate performance.
The present invention is a kind of preparation method of nitrogen-doped carbon supported cobaltosic oxide electrode material, and its step is：
（1）Mixing：In mass ratio 10:1-100:1 weighs carbon source and cobalt source is placed in mortar, and sticky liquid is obtained after ground and mixed State mixture；
（2）Carbonization：Above-mentioned liquefied mixture is put into tube furnace, 100-400 DEG C of insulation 10- is warming up under an argon atmosphere 60min, then 600-1600 DEG C of insulation 60-360min is warming up to, room temperature is cooled to, presoma is obtained；
（3）Oxidation：Room is cooled to after above-mentioned presoma is warming up into 200-700 DEG C, insulation 20-120min in air atmosphere Temperature, is made nitrogen-doped carbon supported cobaltosic oxide electrode material.
Usefulness of the present invention is：Cobaltosic oxide electrode material is modified by the composition for regulating and controlling carbon base body. Using the ionic liquid for containing nitrogen as carbon source, cobalt salt is mixed with ionic liquid first, salt solubility is in ionic liquid In or chemically react with ionic liquid, it is ensured that cobalt source is uniformly mixed with carbon source in molecular level；Again through high temperature cabonization, oxygen Nitrogen-doped carbon supported cobaltosic oxide material is obtained after change.This method prepares the letter of nitrogen-doped carbon supported cobaltosic oxide material technology Single, cobaltosic oxide particle is small, good dispersion, and the nitrogen content and cobaltosic oxide load capacity in carbon base body are adjustable.
Brief description of the drawings
Fig. 1 prepares the process chart of nitrogen-doped carbon supported cobaltosic oxide electrode material for the present invention, and Fig. 2 is the present invention The XRD of the nitrogen-doped carbon supported cobaltosic oxide electrode material of preparation, Fig. 3 loads four oxygen for nitrogen-doped carbon prepared by the present invention Change the specific discharge capacity cyclic curve of three cobalt electrode materials.
Embodiment
The present invention is a kind of preparation method of nitrogen-doped carbon supported cobaltosic oxide electrode material, and its step is：
（1）Mixing：In mass ratio 10:1-100:1 weighs carbon source and cobalt source is placed in mortar, and sticky liquid is obtained after ground and mixed State mixture；
（2）Carbonization：Above-mentioned liquefied mixture is put into tube furnace, 100-400 DEG C of insulation 10- is warming up under an argon atmosphere 60min, then 600-1600 DEG C of insulation 60-360min is warming up to, room temperature is cooled to, presoma is obtained；
（3）Oxidation：Room is cooled to after above-mentioned presoma is warming up into 200-700 DEG C, insulation 20-120min in air atmosphere Temperature, is made nitrogen-doped carbon supported cobaltosic oxide electrode material.
Carbon source described in method made above is ionic liquid, specially 1- butyl -3- methyl imidazolium tetrafluoroborates, or Person's 1- butyl -3- methylimidazole dihydric phosphates, either 1- butyl -3- methylimidazolium nitrates or 1- butyl -3- methyl miaows Azoles bromide, either 1- ethyl-3-methylimidazoles bromide or hydroxide 1- butyl -3- methylimidazole salts, or hydroxide 1- ten Dialkyl group -3- methylimidazole salts, either chlorination 1- butyl -3- methylimidazole salts or 1- ethyl-3-methylimidazole dintrile amine Salt, either 1- butyl -3- methylimidazole dintrile amine salt or 1- octyl group -3- methylimidazole dintrile amine salt, or 1- butyl -2, 3- methylimidazole dintrile amine salt, either N- ethylpyridines dintrile amine salt or 1- nitrile propyl group -3- methylimidazole villaumites, or 1- nitrile propyl group -3- methylimidazole dintrile amine salt, either 1- nitriles propyl group -3- methylimidazolium nitrates or 1- pi-allyl -3- butyl Imidazoles dintrile amine salt, either 1- pi-allyls -3- hexyl imidazoliums villaumite or 1- pi-allyl -3- hexyl imidazolium bromides, or above-mentioned The combination of ionic liquid.
Cobalt source described in method made above is cobalt nitrate, either cobalt acetate or acetylacetone cobalt, or cobalt oxalate, Either cobaltous sulfate or cobalt carbonate, or above-mentioned cobalt salt combination.
The present invention is described further with specific embodiment below in conjunction with the accompanying drawings, but the present invention is not limited to following reality Apply example.
Embodiment 1：
20g1- butyl -3- methyl imidazolium tetrafluoroborates and 1g cobalt acetates are placed in after ground and mixed is uniform in mortar and are put into earthenware In crucible, 100 DEG C of insulation 30min are heated under argon gas protection in tube furnace, then are warming up to 700 DEG C of insulation 120min, are cooled to Room temperature；It is warming up to 600 DEG C of insulation 30min in air atmosphere again, is cooled to room temperature, obtains nitrogen-doped carbon supported cobaltosic oxide Electrode material.The electrochemical property test of gained nitrogen-doped carbon supported cobaltosic oxide electrode material is using CR2025 buttons electricity Pond, by the nitrogen-doped carbon supported cobaltosic oxide active material prepared and conductive agent acetylene black, binding agent PVDF（Gather inclined difluoro Ethene）By 8:1:1 is well mixed, and adds appropriate NMP（1-METHYLPYRROLIDONE）Grind uniform in agate mortar, formed sticky Colloidal mixture, be then uniformly coated on the thick copper foils of 0.02mm, be placed in 100 DEG C of vacuum drying 10h, be washed into diameter 9mm Disk, metal lithium sheet is used to electrode, electrolyte uses 1mol.L-LiPF6/EC:DMC(1:1), wherein EC is ethylene carbonate Ester, DMC is dimethyl carbonate, and barrier film uses celgard2400 barrier films, assembled in the glove box full of inert atmosphere. The battery assembled carries out charge-discharge performance test with blue electric battery test system.Charge-discharge magnification be 0.1C under the conditions of, material Initial discharge specific capacity is 866.5mAh/g, and 20 capacity of circulation are maintained at 457.3 mAh/g.
Embodiment 2：
20g1- butyl -3- methylimidazole dintrile ammonium salts and 1g cobalt acetates are placed in after ground and mixed is uniform in mortar and are put into crucible It is interior, 100 DEG C of insulation 30min are heated under argon gas protection in tube furnace, then 900 DEG C of insulation 120min are warming up to, it is cooled to room Temperature；It is warming up to 450 DEG C of insulation 45min in air atmosphere again, is cooled to room temperature, obtains nitrogen-doped carbon supported cobaltosic oxide electricity Pole material（XRD is shown in accompanying drawing 2）.According to the method assembled battery of embodiment 1, tested, charge-discharge magnification be 0.1C under the conditions of, Material initial discharge specific capacity is 904.2mAh/g, and 20 capacity of circulation are maintained at 679.3 mAh/g（See accompanying drawing 3）.
Embodiment 3：
100g1- butyl -3- methylimidazoles dihydric phosphate and 1g cobalt acetates are placed in after ground and mixed is uniform in mortar and are put into earthenware In crucible, 100 DEG C of insulation 30min are heated under argon gas protection in tube furnace, then are warming up to 900 DEG C of insulation 120min, are cooled to Room temperature；It is warming up to 450 DEG C of insulation 45min in air atmosphere again, is cooled to room temperature, obtains nitrogen-doped carbon supported cobaltosic oxide Electrode material.According to the method assembled battery of embodiment 1, tested, charge-discharge magnification is under the conditions of 0.1C, material is initially put Electric specific capacity is 824.8mAh/g, and 20 capacity of circulation are maintained at 459.5mAh/g.
Embodiment 4：
By 15g1- butyl -2,3- methylimidazole dintrile amine salt, 15g hydroxide 1- butyl -3- methylimidazole salts and 1g cobalt nitrates It is placed in after ground and mixed is uniform in mortar and is put into crucible, is heated to 150 DEG C of insulation 30min under argon gas protection in tube furnace, 1000 DEG C of insulation 120min are warming up to again, are cooled to room temperature；It is warming up to 450 DEG C of insulation 60min in air atmosphere again, is cooled to Room temperature, obtains nitrogen-doped carbon supported cobaltosic oxide electrode material.According to the method assembled battery of embodiment 1, tested, filled Discharge-rate is under the conditions of 0.1C, material initial discharge specific capacity is 1024.3mAh/g, and 20 capacity of circulation are maintained at 639.2mAh/g。
Embodiment 5：
15g N- ethylpyridine dintrile amine salt, 15g hydroxide 1- butyl -3- methylimidazole salts and 1g cobalt nitrates are placed in mortar It is put into after ground and mixed is uniform in crucible, is heated to 150 DEG C of insulation 30min under argon gas protection in tube furnace, then be warming up to 1000 DEG C of insulation 120min, are cooled to room temperature；It is warming up to 450 DEG C of insulation 60min in air atmosphere again, is cooled to room temperature, obtains To nitrogen-doped carbon supported cobaltosic oxide electrode material.According to the method assembled battery of embodiment 1, tested, discharge and recharge times Rate is under the conditions of 0.1C, material initial discharge specific capacity is 624.3mAh/g, and 20 capacity of circulation are maintained at 369.2mAh/g.
Embodiment 6：
30g 1- nitriles propyl group -3- methylimidazole villaumites and 3g cobalt acetates are placed in after ground and mixed is uniform in mortar and are put into crucible It is interior, 150 DEG C of insulation 30min are heated under argon gas protection in tube furnace, then 1000 DEG C of insulation 120min are warming up to, it is cooled to room Temperature；It is warming up to 450 DEG C of insulation 60min in air atmosphere again, is cooled to room temperature, obtains nitrogen-doped carbon supported cobaltosic oxide electricity Pole material.According to the method assembled battery of embodiment 1, tested, charge-discharge magnification be 0.1C under the conditions of, material initial discharge Specific capacity is 986.7mAh/g, and 20 capacity of circulation are maintained at 714.7mAh/g.
Embodiment 7：
20g1- butyl -3- methyl imidazolium tetrafluoroborates and 1g cobaltous sulfates are placed in after ground and mixed is uniform in mortar and are put into earthenware In crucible, 100 DEG C of insulation 30min are heated under argon gas protection in tube furnace, then are warming up to 800 DEG C of insulation 120min, are cooled to Room temperature；It is warming up to 600 DEG C of insulation 30min in air atmosphere again, is cooled to room temperature, obtains nitrogen-doped carbon supported cobaltosic oxide Electrode material.According to the method assembled battery of embodiment 1, tested, charge-discharge magnification is under the conditions of 0.1C, material is initially put Electric specific capacity is 486.7mAh/g, and 20 capacity of circulation are maintained at 312.2mAh/g.

Claims (3)

1. a kind of preparation method of nitrogen-doped carbon supported cobaltosic oxide electrode material, it is characterised in that its step is：
（1）Mixing：In mass ratio 10:1-100:1 weighs carbon source and cobalt source is placed in mortar, and sticky liquid is obtained after ground and mixed State mixture；
（2）Carbonization：Above-mentioned liquefied mixture is put into tube furnace, 100-400 DEG C of insulation 10- is warming up under an argon atmosphere 60min, then 600-1600 DEG C of insulation 60-360min is warming up to, room temperature is cooled to, presoma is obtained；
（3）Oxidation：Room is cooled to after above-mentioned presoma is warming up into 200-700 DEG C, insulation 20-120min in air atmosphere Temperature, is made nitrogen-doped carbon supported cobaltosic oxide electrode material.
2. the preparation method of nitrogen-doped carbon supported cobaltosic oxide electrode material according to claim 1, it is characterised in that Described carbon source is ionic liquid, specially 1- butyl -3- methyl imidazolium tetrafluoroborates, or 1- butyl -3- methylimidazoles Dihydric phosphate, either 1- butyl -3- methylimidazolium nitrates or 1- butyl -3- methylimidazole bromides, or 1- ethyls - 3- methylimidazole bromides, either hydroxide 1- butyl -3- methylimidazole salts or hydroxide 1- dodecyl -3- methylimidazoles Salt, either chlorination 1- butyl -3- methylimidazole salts or 1- ethyl-3-methylimidazole dintrile amine salt, or 1- butyl -3- first Base imidazoles dintrile amine salt, either 1- octyl groups -3- methylimidazole dintrile amine salt or 1- butyl -2,3- methylimidazole dintrile amine Salt, either N- ethylpyridines dintrile amine salt or 1- nitrile propyl group -3- methylimidazole villaumites, or 1- nitrile propyl group -3- methylimidazoles Dintrile amine salt, either 1- nitriles propyl group -3- methylimidazolium nitrates or 1- pi-allyl -3- butyl imidazole dintrile amine salt, or 1- Pi-allyl -3- hexyl imidazolium villaumites, the either combination of 1- pi-allyls -3- hexyl imidazoliums bromide or above-mentioned ionic liquid.
3. the preparation method of nitrogen-doped carbon supported cobaltosic oxide electrode material according to claim 1, it is characterised in that Described cobalt source is cobalt nitrate, either cobalt acetate or acetylacetone cobalt, either cobalt oxalate or cobaltous sulfate, or carbonic acid Cobalt, or above-mentioned cobalt salt combination.
CN201710440352.2A 2017-06-13 2017-06-13 A kind of preparation method of nitrogen-doped carbon supported cobaltosic oxide electrode material Pending CN107017404A (en)

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CN109378473A (en) * 2018-08-20 2019-02-22 中国科学院兰州化学物理研究所 The modified carbon-supported copper catalyst of nitrogen and its application in terms of cell positive material
CN110010878A (en) * 2019-04-17 2019-07-12 安徽大学 The porous carbon coating Co of N doping3O4Composite nano materials, preparation method and applications
CN111261883A (en) * 2020-02-21 2020-06-09 河北工业大学 Preparation method and application of ionic liquid functionalized graphene oxide loaded nano cobaltosic oxide composite material
CN111490235A (en) * 2019-01-29 2020-08-04 中国科学院上海硅酸盐研究所 Micron-particle high-capacity lithium ion battery cathode material based on conversion reaction and preparation method and application thereof
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CN108128765A (en) * 2017-12-26 2018-06-08 贵州大学 Prepare method and the application of nitrogen-doped porous carbon material
CN108128765B (en) * 2017-12-26 2021-04-30 贵州大学 Method for preparing nitrogen-doped porous carbon material and application
CN109004189A (en) * 2018-07-10 2018-12-14 河北师范大学 A method of nickel compound of the calcining containing ionic liquid prepares lithium cell cathode material
CN109378473A (en) * 2018-08-20 2019-02-22 中国科学院兰州化学物理研究所 The modified carbon-supported copper catalyst of nitrogen and its application in terms of cell positive material
CN109065369B (en) * 2018-09-06 2020-12-18 山西农业大学 One-dimensional cobaltosic oxide/carbon nano composite material and preparation method and application thereof
CN109065369A (en) * 2018-09-06 2018-12-21 山西农业大学 A kind of one-dimensional cobaltosic oxide/carbon nano-composite material and its preparation method and application
CN111490235A (en) * 2019-01-29 2020-08-04 中国科学院上海硅酸盐研究所 Micron-particle high-capacity lithium ion battery cathode material based on conversion reaction and preparation method and application thereof
CN111490235B (en) * 2019-01-29 2021-08-06 中国科学院上海硅酸盐研究所 Micron-particle high-capacity lithium ion battery cathode material based on conversion reaction and preparation method and application thereof
CN110010878A (en) * 2019-04-17 2019-07-12 安徽大学 The porous carbon coating Co of N doping3O4Composite nano materials, preparation method and applications
CN111261883A (en) * 2020-02-21 2020-06-09 河北工业大学 Preparation method and application of ionic liquid functionalized graphene oxide loaded nano cobaltosic oxide composite material
CN111261883B (en) * 2020-02-21 2022-08-23 河北工业大学 Preparation method and application of ionic liquid functionalized graphene oxide loaded nano cobaltosic oxide composite material
CN111554520A (en) * 2020-05-15 2020-08-18 中国科学院宁波材料技术与工程研究所 Cobaltosic oxide quantum dot @ carbon composite electrode material and preparation method thereof
CN114772653A (en) * 2022-03-11 2022-07-22 广东邦普循环科技有限公司 Nitrogen-doped hollow cobaltosic oxide and preparation method and application thereof
CN115893509A (en) * 2022-11-04 2023-04-04 洛阳理工学院 Preparation method of cobaltosic oxide/nitrogen-doped carbon composite material for lithium ion battery cathode material

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Application publication date: 20170804