CN106169381A - A kind of synthetic method constructing the azotized carbon nano pipe with electrochemical capacitance performance based on ZIF 67 - Google Patents
A kind of synthetic method constructing the azotized carbon nano pipe with electrochemical capacitance performance based on ZIF 67 Download PDFInfo
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- CN106169381A CN106169381A CN201610596681.1A CN201610596681A CN106169381A CN 106169381 A CN106169381 A CN 106169381A CN 201610596681 A CN201610596681 A CN 201610596681A CN 106169381 A CN106169381 A CN 106169381A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 34
- 238000010189 synthetic method Methods 0.000 title claims abstract 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 230000001681 protective effect Effects 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 235000013495 cobalt Nutrition 0.000 claims description 14
- 229910017052 cobalt Inorganic materials 0.000 claims description 12
- 239000010941 cobalt Substances 0.000 claims description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 238000003763 carbonization Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 6
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000004570 mortar (masonry) Substances 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000012621 metal-organic framework Substances 0.000 abstract description 13
- 230000005540 biological transmission Effects 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 7
- 238000004146 energy storage Methods 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 238000009432 framing Methods 0.000 abstract description 3
- 239000011232 storage material Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 8
- 238000010586 diagram Methods 0.000 description 6
- 239000007772 electrode material Substances 0.000 description 4
- 241001597008 Nomeidae Species 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 238000001994 activation Methods 0.000 description 3
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000013153 zeolitic imidazolate framework Substances 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000005255 carburizing Methods 0.000 description 1
- 238000009795 derivation Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- 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
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Carbon And Carbon Compounds (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
A kind of synthetic method constructing the azotized carbon nano pipe with electrochemical capacitance performance based on ZIF 67, belongs to technical field prepared by electrochemical capacitance energy storage material.Under nitrogen protective condition, with ZIF 67 as template, construct by it is carried out high temperature cabonization there is the azotized carbon nano pipe of good electrochemical activity.Specific surface area high for presoma MOFs, good framing structure is maintained based on this azotized carbon nano pipe, and then the beneficially transmission of electronics and promote energy conversion and energy-storage property, therefore there is good electro-chemical activity.
Description
Technical field
The invention belongs to technical field prepared by electrochemical capacitance energy storage material, technology relates to metal-organic framework (Metal-
Organic frameworks, MOFs) material and the preparation method of derivant thereof, particularly construct with MOFs and there is good electric capacity
Constructing of performance carbon nanotube electrode material.
Background technology
In recent years, energy resource consumption increasingly sharpens and environmental crisis promotes people to design and develops novel energy storage and conversion
Device.Ultracapacitor (supercapacitor, SC) is as a kind of novel energy-storing between traditional capacitor and battery
Device, has the plurality of advantages such as efficiency for charge-discharge is fast, power density is high, length in service life, and then at electric automobile, energy
The various fields such as work, flexible electronic device has important using value.Wherein, double layer capacitor is to utilize electrode and electricity
Solving the interfacial electric double layer electric capacity formed between matter and store energy, electrode material is typically by the stable and electrically conductive property of electrochemical properties
Strong carbon-based material such as activated carbon, Graphene, CNT etc. are constituted.Current research shows material with carbon element is carried out nitrogen, sulfur or phosphorus
Doping can effectively promote the electrochemical energy storage character of carbon-based material.But, how material with carbon element internal structure is uniformly mixed
The miscellaneous many that still exists is challenged.
MOFs is the holey framing structure formed by self assembly with organic ligand by metal ion or ion cluster
Material.The features such as its high specific surface area, abundant porosity, multifarious structure make it store at gas, are catalyzed, sense,
The fields such as biomedicine have potential using value.In recent years, along with deepening continuously of research, it is presoma based on MOFs
The synthesis ad hoc structure pattern derivant such as electrode material such as carbon, metal-oxide is gradually applied to lithium ion battery, fuel electricity
In the electrochemical energy storing device such as pond and SC.This be due to MOFs derivant electrode maintain high for presoma MOFs specific surface area,
Good framing structure, abundant avtive spot, and then beneficially electronics transmission and promote energy conversion and energy-storage property.So
And, construct the CNT with good electrochemical activity about MOFs for the report of SCs and but have no report, and many MOFs
Therein contains substantial amounts of nitrogen element, is expected to obtain by derivation process with MOFs for template and has good electrochemical activity
Energy storage electrode material.
Summary of the invention
Object of the present invention is to provide a kind of with ZIF-67 (Zeolitic imidazolate frameworks,
ZIFs) it is that template is constructed and had good electrochemical activity azotized carbon nano tube material.
Mainly comprise the steps that
(1) synthesis of ZIF-67: be stirred at room temperature under state, is dissolved in methanol by 2-methylimidazole and cabaltous nitrate hexahydrate,
Room temperature stands 12～36h, with methanol washing, activation, vacuum drying after mixed liquor is centrifugal, obtains ZIF-67；
(2) carbonization of ZIF-67: the ZIF-67 of preparation in step (1) is placed in mortar and is ground (such as 5min), and nitrogen is protected
Under the conditions of protecting, it is warming up to 700～900 DEG C of carbonizations 2～6h with the heating rate of 2～5 DEG C/min, obtains the azotized carbon nano of cobalt doped
Pipe；
(3) purification of azotized carbon nano pipe: the azotized carbon nano pipe of the cobalt doped of preparation in step (2) is dissolved in 8～
Being acidified 5～32h removal metallic cobalts in the hydrochloric acid solution of 12mol/L, with deionized water and absolute ethanol washing after being centrifuged, vacuum is done
Dry, obtain highly purified azotized carbon nano pipe.
In step (1), 2-methylimidazole, the mol ratio of cabaltous nitrate hexahydrate are preferably 40:9, room temperature time of repose be 12～
36h。
In step (2), carburizing temperature is 700～900 DEG C, and carbonization time is 2～6h.
In step (3), concentration of hydrochloric acid is 8～12mol/L, and acidificatoin time is 5～32h.
The present invention is under nitrogen protective condition, with ZIF-67 as template, has been constructed by high temperature cabonization and has had good electrification
Learn the azotized carbon nano pipe of activity.Preparation method of the present invention is simple, easy to implement.The azotized carbon nano pipe of preparation maintains forerunner
Specific surface area high for body MOFs, abundant hole characteristic, so beneficially electronics transmission and promote energy conversion and energy-storage property,
Therefore there is good electro-chemical activity.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope schematic diagram of the azotized carbon nano pipe of cobalt doped in present example.
Fig. 2 is the transmission electron microscope schematic diagram of the azotized carbon nano pipe of cobalt doped in present example.
Fig. 3 is the transmission electron microscope schematic diagram of azotized carbon nano pipe in present example.
Fig. 4 is the charging and discharging curve figure of azotized carbon nano pipe in present example.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described, but the present invention is not limited to following example.
Embodiment 1
The first step: be stirred at room temperature under state, weighs 0.328g 2-methylimidazole and 0.249g cabaltous nitrate hexahydrate dissolves
In 25mL methanol, room temperature stands 24h, with methanol washing, activation after mixed liquor is centrifugal, is vacuum dried 8h, obtains ZIF-67 at 60 DEG C.
Second step: weigh the ZIF-67 of preparation in 100mg step one and be placed in mortar and grind 5min, nitrogen protective condition
Under, it is warming up to 800 DEG C of carbonization 3h with the heating rate of 2 DEG C/min, obtains the azotized carbon nano pipe of cobalt doped.
3rd step: weigh the azotized carbon nano pipe of the cobalt doped of preparation in 25mg step 2 and be dissolved in 30mL hydrochloric acid solution
(12mol/L) acidifying 24h, gained precipitate with deionized water and absolute ethanol washing after centrifugation, is vacuum dried 8h at 60 DEG C,
Obtain highly purified azotized carbon nano pipe.
Embodiment 2
The first step: be stirred at room temperature under state, weighs 0.328g 2-methylimidazole and 0.249g cabaltous nitrate hexahydrate dissolves
In 25mL methanol, room temperature stands 32h, with methanol washing, activation after mixed liquor is centrifugal, is vacuum dried 8h, obtains ZIF-67 at 60 DEG C.
Second step: weigh the ZIF-67 of preparation in 100mg step one and be placed in mortar and grind 5min, nitrogen protective condition
Under, it is warming up to 850 DEG C of carbonization 3h with the heating rate of 2 DEG C/min, obtains the azotized carbon nano pipe of cobalt doped.
3rd step: weigh the azotized carbon nano pipe of the cobalt doped of preparation in 25mg step 2 and be dissolved in 30mL hydrochloric acid solution
(12mol/L) acidifying 32h, gained precipitate with deionized water and absolute ethanol washing after centrifugation, is vacuum dried 8h at 60 DEG C,
Obtain highly purified azotized carbon nano pipe.
The test result of the material of above-described embodiment gained is identical, is specifically shown in following:
(1) material morphology characterizes:
Fig. 1 is the scanning electron microscope schematic diagram of the azotized carbon nano pipe of cobalt doped, and Fig. 2 is the azotized carbon nano pipe of cobalt doped
Transmission electron microscope schematic diagram, Fig. 3 is the transmission electron microscope schematic diagram of azotized carbon nano pipe.
(2) material charge-discharge performance characterizes:
In Fig. 4, curve 1 and curve 2 are ZIF-67 powder respectively and azotized carbon nano pipe is 1A/g in electric current density, electrolysis
Liquid is the discharge curve in 1mol/L KOH solution.
Foregoing is the preferred embodiments of the present invention, but the present invention should not be limited to this example disclosure.Institute
With all without departing from the equivalence completed under spirit disclosed in this invention or amendment, both fall within the scope of protection of the invention.
Claims (3)
1. the synthetic method constructing the azotized carbon nano pipe with electrochemical capacitance performance based on ZIF-67, it is characterised in that bag
Include following steps:
(1) synthesis of ZIF-67: be stirred at room temperature under state, is dissolved in methanol, room temperature by 2-methylimidazole and cabaltous nitrate hexahydrate
Stand 12～36h, wash with methanol, activate, be vacuum dried after mixed liquor is centrifugal, obtain ZIF-67；
(2) carbonization of ZIF-67: the ZIF-67 of preparation in step (1) is placed in mortar and grinds, under nitrogen protective condition, with 2
～the heating rate of 5 DEG C/min is warming up to 700～900 DEG C of carbonizations 2～6h, obtain the azotized carbon nano pipe of cobalt doped；
(3) purification of azotized carbon nano pipe: the azotized carbon nano pipe of the cobalt doped of preparation in step (2) is dissolved in 8～12mol/L
Hydrochloric acid solution in be acidified 5～32h removal metallic cobalts, centrifugal after with deionized water and absolute ethanol washing, vacuum drying, obtain high
The azotized carbon nano pipe of purity.
2. according to the preparation method of claim 1, it is characterised in that 2-methylimidazole in step (1), the rubbing of cabaltous nitrate hexahydrate
That ratio is 40:9.
3. the azotized carbon nano pipe prepared according to the method for claim 1 or 2.
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106904596A (en) * | 2017-03-06 | 2017-06-30 | 武汉理工大学 | The nano structural material of the CNT assembling prepared based on metal organic framework compound low temperature pyrogenation and its preparation and application |
| CN107394214A (en) * | 2017-07-13 | 2017-11-24 | 北京化工大学常州先进材料研究院 | The preparation and application of the nitrogen co-doped porous carbon microsphere material of cobalt |
| CN108328706A (en) * | 2018-01-15 | 2018-07-27 | 浙江工业大学 | A kind of MOF derives the preparation and application of porous carbon/graphene combination electrode material |
| CN109256567A (en) * | 2018-08-27 | 2019-01-22 | 暨南大学 | A kind of preparation method of transition metal/nitrogen doped corrugated carbon nanotube |
| CN109616333A (en) * | 2018-12-07 | 2019-04-12 | 武汉工程大学 | A kind of nitrogen-doped carbon nanometer pipe/cobaltosic oxide composite material and preparation method thereof |
| CN109637835A (en) * | 2018-12-07 | 2019-04-16 | 武汉工程大学 | A kind of nitrogen-doped carbon nanometer pipe/cobaltosic oxide composite aerogel and preparation method thereof |
| CN109999822A (en) * | 2019-04-02 | 2019-07-12 | 福建师范大学 | A kind of preparation of the cobaltosic oxide catalyst of carbon nanotube loaded molybdenum doping |
| CN110170325A (en) * | 2019-06-02 | 2019-08-27 | 上海纳米技术及应用国家工程研究中心有限公司 | Hollow structure cobalt/cobalt oxide/carbon nanotube preparation administered for propane and products thereof and application |
| CN110586041A (en) * | 2019-09-19 | 2019-12-20 | 山东省分析测试中心 | Perfluoroalkyl compound extraction and analysis method based on MOFs stripping graphite phase nitrogen carbide adsorbent |
| CN110591388A (en) * | 2019-08-22 | 2019-12-20 | 安徽建筑大学 | Flame-retardant smoke suppressant containing cobalt, nitrogen and silicon and preparation method thereof |
| CN110854392A (en) * | 2019-10-28 | 2020-02-28 | 东南大学 | Metal organic framework-based cereal-grain-shaped carbon material and preparation and application thereof |
| CN111672474A (en) * | 2020-06-28 | 2020-09-18 | 福州大学 | Magnetic nitrogen-doped carbon oxide nanotube material and preparation method and application thereof |
| CN111725502A (en) * | 2019-03-18 | 2020-09-29 | 新奥科技发展有限公司 | Positive electrode material and preparation method thereof, positive electrode piece and ion battery |
| CN113247869A (en) * | 2021-05-19 | 2021-08-13 | 东南大学 | Preparation method of carbon nitride material, carbon nitride material prepared by preparation method and application of carbon nitride material |
| CN113594474A (en) * | 2021-07-05 | 2021-11-02 | 河南师范大学 | Preparation method and application of self-catalytic growth Zn/Co-N-C carbon nanotube oxygen reduction catalyst |
| CN114261950A (en) * | 2021-12-20 | 2022-04-01 | 徐州工程学院 | Tubular cobalt hybrid g-C3N4Material, microwave synthesis method thereof and application of material in field of super capacitor |
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| CN106904596A (en) * | 2017-03-06 | 2017-06-30 | 武汉理工大学 | The nano structural material of the CNT assembling prepared based on metal organic framework compound low temperature pyrogenation and its preparation and application |
| CN107394214B (en) * | 2017-07-13 | 2020-05-19 | 北京化工大学常州先进材料研究院 | Preparation and application of cobalt-nitrogen co-doped porous carbon microsphere material |
| CN107394214A (en) * | 2017-07-13 | 2017-11-24 | 北京化工大学常州先进材料研究院 | The preparation and application of the nitrogen co-doped porous carbon microsphere material of cobalt |
| CN108328706A (en) * | 2018-01-15 | 2018-07-27 | 浙江工业大学 | A kind of MOF derives the preparation and application of porous carbon/graphene combination electrode material |
| CN108328706B (en) * | 2018-01-15 | 2021-12-21 | 浙江工业大学 | Preparation and application of MOF-derived porous carbon/graphene composite electrode material |
| CN109256567A (en) * | 2018-08-27 | 2019-01-22 | 暨南大学 | A kind of preparation method of transition metal/nitrogen doped corrugated carbon nanotube |
| CN109637835B (en) * | 2018-12-07 | 2021-08-13 | 武汉工程大学 | Nitrogen-doped carbon nanotube/cobaltosic oxide composite aerogel and preparation method thereof |
| CN109616333A (en) * | 2018-12-07 | 2019-04-12 | 武汉工程大学 | A kind of nitrogen-doped carbon nanometer pipe/cobaltosic oxide composite material and preparation method thereof |
| CN109637835A (en) * | 2018-12-07 | 2019-04-16 | 武汉工程大学 | A kind of nitrogen-doped carbon nanometer pipe/cobaltosic oxide composite aerogel and preparation method thereof |
| CN111725502A (en) * | 2019-03-18 | 2020-09-29 | 新奥科技发展有限公司 | Positive electrode material and preparation method thereof, positive electrode piece and ion battery |
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