CN108695507A - A kind of preparation method and applications of the porous cobaltosic oxide nano particle of carbon coating - Google Patents
A kind of preparation method and applications of the porous cobaltosic oxide nano particle of carbon coating Download PDFInfo
- Publication number
- CN108695507A CN108695507A CN201810617115.3A CN201810617115A CN108695507A CN 108695507 A CN108695507 A CN 108695507A CN 201810617115 A CN201810617115 A CN 201810617115A CN 108695507 A CN108695507 A CN 108695507A
- Authority
- CN
- China
- Prior art keywords
- cobaltosic oxide
- nano particle
- porous cobaltosic
- oxide nano
- carbon coating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 title claims abstract description 139
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 54
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 41
- 239000011248 coating agent Substances 0.000 title claims abstract description 34
- 238000000576 coating method Methods 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000227 grinding Methods 0.000 claims abstract description 9
- 239000007772 electrode material Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 239000002002 slurry Substances 0.000 claims abstract description 7
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 6
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 6
- 235000019441 ethanol Nutrition 0.000 claims abstract description 5
- 230000001681 protective effect Effects 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000004090 dissolution Methods 0.000 claims abstract description 3
- 238000001354 calcination Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 6
- 238000003801 milling Methods 0.000 claims description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- 229920001661 Chitosan Polymers 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 3
- 238000003763 carbonization Methods 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 238000005868 electrolysis reaction Methods 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims 1
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 description 2
- ZDYUUBIMAGBMPY-UHFFFAOYSA-N oxalic acid;hydrate Chemical class O.OC(=O)C(O)=O ZDYUUBIMAGBMPY-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000004900 laundering Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- H01M4/366—Composites as layered products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B01J35/23—
-
- B01J35/397—
-
- B01J35/613—
-
- 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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- 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
- 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
- H01G11/84—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
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
-
- 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
Application in terms of the present invention relates to a kind of preparation method of the porous cobaltosic oxide nano particle of carbon coating and its as electrode material.This approach includes the following steps:Step(1), cobalt nitrate and oxalic acid are placed in mixed grinding, obtain the slurry of pink;It is dry after gained slurry is washed, it is then calcined in air atmosphere, obtains porous cobaltosic oxide;Step(2), by a small amount of water dissolution of carbon source presoma, ethyl alcohol grinding is then added together with porous cobaltosic oxide uniformly, and gained mixture is put into baking oven and is dried;Step(3), by step(2)Gained mixture is transferred in temperature programming tube furnace, up to carbon-coated porous cobaltosic oxide nano particle after heating charing under protective atmosphere.The preparation method of the electrode material is simple, and cost is relatively low, is applied in lithium ion battery, compared with simple cobaltosic oxide nano particle, shows excellent cycle performance and high rate performance.
Description
Technical field
The invention belongs to field of nano material preparation, more particularly to a kind of porous cobaltosic oxide nano particle of carbon coating
Preparation method and its application in terms of lithium ion battery electrode material.
Background technology
The continuous exploitation and use of petroleum resources have caused energy crisis and environmental pollution, become what the whole world was paid close attention to jointly
Hot topic.Currently, the scientific research institution of all parts of the world and experts and scholars are developing and are exploring new energy or new energy technology one after another,
The energy and environment is set to go on the road of sustainable development.Wherein, development of the lithium ion battery in terms of energy storage is increasingly closed
Note has many advantages, such as that big specific capacity, light weight, service life are long relative to conventional batteries (lead accumulator, nickel-cadmium cell etc.).
But with social development, the requirement to battery performance is also being continuously improved, and lithium ion battery is also constantly improving.
Although negative material of the graphite as commercial Li-ion battery is currently mainly used, its specific capacity is low, times
Rate poor performance makes the development of lithium ion battery be limited accordingly.For transition metal oxide since it is derived from a wealth of sources, price is low
Advantages, the applications in terms of lithium ion battery such as honest and clean and specific capacity is big cause the extensive concern of researcher.Cobalt base oxide is negative
Pole material is due to its higher specific capacity (890mA h g-1) cause the extensive research interest of people.But themselves
Low conductivity and occurs the shortcomings of serious volume expansion in charge and discharge process and limit it in high performance energy memory device
In application.
Invention content
The technical problem to be solved by the present invention is to provide a kind of carbon coating in view of the deficiency of the prior art
The preparation method of porous cobaltosic oxide nano particle can improve the electric conductivity of material and alleviate the body in charge and discharge process
Product expansion issues.
The present invention be solve the problems, such as it is set forth above used by technical solution be:
A kind of preparation method of the porous cobaltosic oxide nano particle of carbon coating, including following steps:
Step (1), the preparation of cobaltosic oxide:Cobalt nitrate and oxalic acid are placed in mixed grinding, obtain the pulpous state of pink
Object;It is dry after gained slurry is washed, it is then carbonized in air atmosphere, obtains porous cobaltosic oxide;
Step (2), the preparation of the porous cobaltosic oxide precursor of carbon coating:By a small amount of water dissolution of carbon source presoma, so
It is uniform that ethyl alcohol grinding is added together with porous cobaltosic oxide afterwards, takes away the moisture in mixture using the volatilization of ethyl alcohol, and will
Gained mixture, which is put into baking oven, dries;
Mixture obtained by step (2) is transferred in temperature programming tube furnace by step (3), and heat up charcoal under protective atmosphere
Up to carbon-coated porous cobaltosic oxide nano particle after change.
It is further preferred that cobalt nitrate and oxalic acid mole are 1 in step (1):(1-2), preferred optimum mole ratio are
1:1.5。
It is further preferred that milling time is 1.0-1.5 hours in step (1).
It is further preferred that calcination temperature described in step (1) is 400-600 DEG C, heating rate is 2-5 DEG C of min-1, forge
The burning time is 2-3h.
It is further preferred that the presoma described in step (2) is glucose, chitosan, the glucides such as sucrose.
It is further preferred that the mass ratio of the porous cobaltosic oxide in step (2) obtained by carbon source presoma and step (1)
For (0.5-1.5):(4-6), preferred optimum quality ratio are 1:5.
It is further preferred that step (2) described milling time is 0.5-1.0h.
It is further preferred that the protective atmosphere described in step (3) is nitrogen or inert gas etc..
It is further preferred that step (3) described carbonization temperature is 350-450 DEG C, heating rate is 2-5 DEG C of min-1, calcining
Time is 2-3h.
Another object of the present invention is to provide the above method prepare the porous cobaltosic oxide nano particle of carbon coating and
Its application in terms of electrode material can be applied to the electrodes such as lithium battery, electrolysis aquatic products hydrogen catalysis electrode material, ultracapacitor
Material.
The present invention has following advantage compared with prior art:
First, the present invention is by nano-structured by porous cobaltosic oxide nano particle, and carries out carbon coating to it, carries
Volume expansion problem in its high electric conductivity and alleviation charge and discharge process as electrode material.
Moreover, carbon-coated cobaltosic oxide nano particle has a porous structure, one side electrolyte can with it is more
Active contacts, alleviate influence of the expansion to electrode of volume in charge and discharge process, the introducing of another aspect carbon improves
The conductivity of material, these are all conducive to the cycle performance and high rate performance that improve battery.
Furthermore the present invention obtains carbon-coated porous cobaltosic oxide nano by simply grinding with low-temperature carbonization
, it is carried out under low temperature, at low cost, preparation process is simple, and experimental period is short, reproducible, is easy to mass produce.
Description of the drawings
Fig. 1 is the XRD diagram of cobaltosic oxide and carbon coating cobaltosic oxide in embodiment 1.
(a) is the scanning electron microscope diagram of the porous cobaltosic oxide of embodiment 1 in Fig. 2, is (b) carbon of embodiment 1
The scanning electron microscope diagram of coated porous cobaltosic oxide, it is (c) aobvious for the transmitted electron of the porous cobaltosic oxide of embodiment 1
Micro mirror figure is (d) transmission electron microscope figure of the porous cobaltosic oxide of carbon coating of embodiment 1.
(a) is the nitrogen adsorption desorption curve of porous cobaltosic oxide in embodiment 1 in Fig. 3, is (b) carbon packet in embodiment 1
Cover the nitrogen adsorption desorption curve of porous cobaltosic oxide.
(a) is that the electric discharge of the cycle of porous cobaltosic oxide and the porous cobaltosic oxide of carbon coating is bent in embodiment 1 in Fig. 4
Line is (b) rate discharge curves of porous cobaltosic oxide and the porous cobaltosic oxide of carbon coating in embodiment 1.
Specific implementation mode
With reference to specific examples and drawings the present invention is described in further detail, but the implementation of the present invention
Flexibly, it is not limited only to the concrete operations mode described in this.
Embodiment 1
A kind of preparation method of the porous cobaltosic oxide nano particle of carbon coating, including following steps:
(1) 10mmol cobalt nitrates are placed in mortar and are ground, then is small by grinding 1 together in 15mmol oxalic acid addition mortar
When, obtain the slurry of pink;Gained slurry is washed and dried with massive laundering, by obtained substance in temperature programming pipe
It is calcined in air atmosphere in formula stove, with 2 DEG C of min-1Heating rate be raised to 400 DEG C of charing 2h after, and with 5 DEG C of min-1Cooling
Rate obtains porous cobaltosic oxide after being cooled to room temperature;
(2) weighing 0.06g glucose a small amount of water is added in mortar makes glucose dissolve, then will be in 0.3g (2) obtained by
Porous cobaltosic oxide be added mortar in grind 0.5h together, absolute ethyl alcohol is added during grinding in right amount, utilizes second
The moisture in mixture is taken away in the volatilization of alcohol, and obtained substance is put into baking oven and is dried;
(3) substance that (2) are dried is put into temperature programming tube furnace in N2Protection under, with 2 DEG C of min-1Heating speed
After rate is raised to 400 DEG C of charing 2h, and with 5 DEG C of min-1Carbon-coated porous four oxidation three to obtain the final product after rate of temperature fall is cooled to room temperature
Cobalt nano-particle.
The performance of carbon-coated porous cobaltosic oxide nano granular materials obtained by the present invention passes through button cell
It measures, battery size CR2032, lithium piece is to electrode, diaphragm Celgard2400, and electrolyte is 1M LiPF6 1:1EC:
DMC (volume ratio), is assembled in the glove box full of argon gas, is tested on new prestige tester.
To porous cobaltosic oxide nano particle (i.e. the product of step (1)), carbon-coated porous cobaltosic oxide
Nano particle ((i.e. the product of step (3))) carries out X-ray diffraction measure respectively, XRD diagram as shown in Figure 1, in 2 θ=31.3 °,
36.9 °, 44.9 °, 59.5 °, 65.4 ° correspond respectively to Co3O4(220), (311), (400), (511), (440) (JCPDS
No.74-1657) diffraction crystal face.
Electricity is scanned respectively to porous cobaltosic oxide nano, carbon-coated porous cobaltosic oxide nano particle
The observation of sub- microscope and transmission electron microscope, the results are shown in Figure 2.It can be seen that four simple oxidations from Fig. 2 (a)
Three cobalt surface smoothers, after carrying out carbon coating to it in Fig. 2 (b), surface becomes rough porous;It can from Fig. 2 (c) and (d)
To be clearly visible the porous structure inside the two, and the size of nano particle is about 200nm.
As shown in Fig. 3 (a) and (b), to porous cobaltosic oxide nano particle, the porous cobaltosic oxide nano of carbon coating
The test that particle carries out specific surface area obtains N2Adsorption desorption curve and graph of pore diameter distribution, porous cobaltosic oxide can be calculated
The specific surface area of the porous cobaltosic oxide nano particle of nano particle, carbon coating is respectively 36.398m2/ g and 58.943m2/ g, carbon
Cladding so that the specific surface area of the porous cobaltosic oxide nano particle of carbon coating is increased.
As shown in Fig. 4 (a) and (b), by porous cobaltosic oxide nano particle, the porous cobaltosic oxide nano of carbon coating
Grain is assembled into button cell and tests its cycle and high rate performance, and the voltage range of impulse electricity is 0.01-3V, the current density of cycle
For 50mA/g.In Fig. 4 (a), it can be seen that the first discharge specific capacity of the porous cobaltosic oxide nano particle of carbon coating is
1801mA h/g, specific capacity stills remain in 422mA h/g after 100 circle of cycle, simple porous four oxidation three under similarity condition
The specific capacity of cobalt nano-particle is only 212mA h/g.Fig. 4 (b) is the high rate performance test to the two, gradual from low current density
It is returned to low current density after increasing to high current density, the specific capacity of the porous cobaltosic oxide nano particle of carbon coating is all than list
Pure porous cobaltosic oxide nano particle is high, and when current density is 1000mA/g, the porous cobaltosic oxide of carbon coating
The specific capacity of nano particle still up to 201mA h/g, shows preferable high rate performance and invertibity.These are integrated, is said
The bright porous cobaltosic oxide nano particle of carbon coating has relatively good performance, can be applied to the negative material of lithium ion battery.
Embodiment 2
The present embodiment difference from Example 1 is:Cabaltous nitrate hexahydrate described in step (1) and two oxalic acid hydrates
Molar ratio be 1:1, other conditions are same as Example 1.
Embodiment 3
The present embodiment difference from Example 1 is:Cabaltous nitrate hexahydrate described in step (1) and two oxalic acid hydrates
Molar ratio be 1:2, other conditions are same as Example 1.
Embodiment 4
The present embodiment difference from Example 1 is:Milling time described in step (1) is 1.5h, other conditions
It is same as Example 1.
Embodiment 5
The present embodiment difference from Example 1 is:Calcination temperature described in step (1) is 500 DEG C, heating rate
For 5 DEG C of min-1, calcination time 2h, other conditions are same as Example 1.
Embodiment 6
The present embodiment difference from Example 1 is:Calcination temperature described in step (1) is 600 DEG C, heating rate
For 5 DEG C of min-1, calcination time is that the other conditions of 3h are same as Example 1.
Embodiment 7
The present embodiment difference from Example 1 is:Presoma described in step (2) is chitosan, other conditions
It is same as Example 1.
Embodiment 8
The present embodiment difference from Example 1 is:Presoma described in step (2) is sucrose, and other conditions are equal
It is same as Example 1.
Embodiment 9
The present embodiment difference from Example 1 is:It is porous obtained by carbon source presoma and step (1) in step (2)
The mass ratio of cobaltosic oxide is 0.5:4, other conditions are same as Example 1.
Embodiment 10
The present embodiment difference from Example 1 is:It is porous obtained by carbon source presoma and step (1) in step (2)
The mass ratio of cobaltosic oxide is 1.5;6, other conditions are same as Example 1.
Embodiment 11
The present embodiment difference from Example 1 is:Milling time described in step (1) is 1h, and other conditions are equal
It is same as Example 1.
Embodiment 12
The present embodiment difference from Example 1 is:Atmosphere described in step (3) is argon gas atmosphere, other conditions
It is same as Example 1.
Embodiment 13
The present embodiment difference from Example 1 is:Calcination temperature described in step (3) is 350 DEG C, heating rate
For 5 DEG C of min-1, calcination time 2h, other conditions are same as Example 1.
Embodiment 14
The present embodiment difference from Example 1 is:Calcination temperature described in step (1) is 450 DEG C, heating rate
For 5 DEG C of min-1, calcination time 3h, other conditions are same as Example 1.
When embodiment 2-14 tests its cycle performance, first discharge specific capacity is all within the scope of 1790-1810mA h/g
Fluctuation, specific capacity stills remain within the scope of 410-430mA h/g after cycle 100 is enclosed;Its high rate performance is tested in current density
For 1000mA/g when, the specific capacity of the porous cobaltosic oxide nano particle of carbon coating is fluctuated within the scope of 190-210mA h/g.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by changes, modifications, substitutions, combinations, simplifications,
Equivalent substitute mode is should be, is included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of the porous cobaltosic oxide nano particle of carbon coating, it is characterised in that including following steps:
Step(1), cobalt nitrate and oxalic acid are placed in mixed grinding, obtain the slurry of pink;After gained slurry is washed
It is dry, it is then carbonized in air atmosphere, obtains porous cobaltosic oxide;
Step(2), by a small amount of water dissolution of carbon source presoma, it is equal that ethyl alcohol grinding is then added together with porous cobaltosic oxide
It is even, and gained mixture is put into baking oven and is dried;
Step(3), by step(2)Gained mixture is transferred in temperature programming tube furnace, under protective atmosphere after heating charing
Up to carbon-coated porous cobaltosic oxide nano particle.
2. a kind of preparation method of the porous cobaltosic oxide nano particle of carbon coating according to claim 1, feature exist
In step(1)Middle cobalt nitrate and oxalic acid mole are 1:(1-2).
3. a kind of preparation method of the porous cobaltosic oxide nano particle of carbon coating according to claim 1, feature exist
In step(1)Middle milling time is 1.0-1.5 hours.
4. a kind of preparation method of the porous cobaltosic oxide nano particle of carbon coating according to claim 1, feature exist
In step(1)Described in calcination temperature be 400-600 DEG C, heating rate be 2-5 DEG C of min-1, calcination time is 2-3 h.
5. a kind of preparation method of the porous cobaltosic oxide nano particle of carbon coating according to claim 1, feature exist
In step(2)The presoma is glucose, chitosan, one or more of sucrose.
6. a kind of preparation method of the porous cobaltosic oxide nano particle of carbon coating according to claim 1, feature exist
In step(2)Middle carbon source presoma and step(1)The mass ratio of the porous cobaltosic oxide of gained is(0.5-1.5):(4-6).
7. a kind of preparation method of the porous cobaltosic oxide nano particle of carbon coating according to claim 1, feature exist
In step(2)The milling time is 0.5-1.0 h.
8. a kind of preparation method of the porous cobaltosic oxide nano particle of carbon coating according to claim 1, feature exist
In step(3)The carbonization temperature is 350-450 DEG C, and heating rate is 2-5 DEG C of min-1, calcination time is 2-3 h.
9. the porous cobaltosic oxide nano particle of carbon coating prepared by claim 1 the method.
10. the porous cobaltosic oxide nano particle of carbon coating described in claim 9 is in electrode material of lithium battery, electrolysis aquatic products hydrogen
Application in terms of catalytic electrode material, ultracapacitor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810617115.3A CN108695507A (en) | 2018-06-15 | 2018-06-15 | A kind of preparation method and applications of the porous cobaltosic oxide nano particle of carbon coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810617115.3A CN108695507A (en) | 2018-06-15 | 2018-06-15 | A kind of preparation method and applications of the porous cobaltosic oxide nano particle of carbon coating |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108695507A true CN108695507A (en) | 2018-10-23 |
Family
ID=63848274
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810617115.3A Pending CN108695507A (en) | 2018-06-15 | 2018-06-15 | A kind of preparation method and applications of the porous cobaltosic oxide nano particle of carbon coating |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108695507A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111740083A (en) * | 2020-06-12 | 2020-10-02 | 新昌县华发机械股份有限公司 | Carbon-coated porous Co3O4Microsphere lithium ion battery cathode material and preparation method thereof |
| CN112436124A (en) * | 2020-11-30 | 2021-03-02 | 安徽师范大学 | Porous cobaltosic oxide/carbonized microcapsule composite material and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4142005A (en) * | 1976-02-27 | 1979-02-27 | The Dow Chemical Company | Process for preparing an electrode for electrolytic cell having a coating of a single metal spinel, Co3 O4 |
| CN102659192A (en) * | 2012-04-27 | 2012-09-12 | 浙江大学 | Cobalt oxide anode material, amorphous carbon coated cobalt oxide anode material and preparation method and application of cobalt oxide anode material and amorphous carbon coated cobalt oxide anode material |
| CN103094559A (en) * | 2013-01-31 | 2013-05-08 | 湘潭大学 | Co3O4/C lithium ion battery cathode material and preparation method thereof |
| CN103274481A (en) * | 2013-05-24 | 2013-09-04 | 中国科学院苏州纳米技术与纳米仿生研究所 | Preparation method based on solid-phase reaction for capacitor electrode material |
| CN104993148A (en) * | 2015-06-16 | 2015-10-21 | 田东 | Synthesizing method for lithium-ion positive electrode material of LiCoO2/C |
| CN105332003A (en) * | 2015-11-30 | 2016-02-17 | 天津理工大学 | Ultrathin nanosheet array electro-catalytic material with nano-porous structure and oxygen vacancies |
-
2018
- 2018-06-15 CN CN201810617115.3A patent/CN108695507A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4142005A (en) * | 1976-02-27 | 1979-02-27 | The Dow Chemical Company | Process for preparing an electrode for electrolytic cell having a coating of a single metal spinel, Co3 O4 |
| CN102659192A (en) * | 2012-04-27 | 2012-09-12 | 浙江大学 | Cobalt oxide anode material, amorphous carbon coated cobalt oxide anode material and preparation method and application of cobalt oxide anode material and amorphous carbon coated cobalt oxide anode material |
| CN103094559A (en) * | 2013-01-31 | 2013-05-08 | 湘潭大学 | Co3O4/C lithium ion battery cathode material and preparation method thereof |
| CN103274481A (en) * | 2013-05-24 | 2013-09-04 | 中国科学院苏州纳米技术与纳米仿生研究所 | Preparation method based on solid-phase reaction for capacitor electrode material |
| CN104993148A (en) * | 2015-06-16 | 2015-10-21 | 田东 | Synthesizing method for lithium-ion positive electrode material of LiCoO2/C |
| CN105332003A (en) * | 2015-11-30 | 2016-02-17 | 天津理工大学 | Ultrathin nanosheet array electro-catalytic material with nano-porous structure and oxygen vacancies |
Non-Patent Citations (1)
| Title |
|---|
| 葛鑫: ""Co3O4的制备及其超级电容性能研究"", 《中国优秀硕士学位论文全文数据库 工程科技II辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111740083A (en) * | 2020-06-12 | 2020-10-02 | 新昌县华发机械股份有限公司 | Carbon-coated porous Co3O4Microsphere lithium ion battery cathode material and preparation method thereof |
| CN112436124A (en) * | 2020-11-30 | 2021-03-02 | 安徽师范大学 | Porous cobaltosic oxide/carbonized microcapsule composite material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110395774B (en) | Preparation method and application of nickel cobaltate porous material | |
| CN110364717B (en) | Spinel type high-entropy oxide electrode material and preparation method thereof | |
| CN110400926A (en) | A kind of nitrogen-doped carbon cladding two-phase is interspersed type nickel cobalt bimetallic selenides electrode material and preparation method thereof | |
| CN101587948B (en) | Preparation method for LiTiO/C compound electrode material | |
| CN106450211B (en) | A kind of lithium-rich manganese-based anode material and preparation method thereof of surface covered composite yarn | |
| CN103794777B (en) | A kind of preparation method of surface coated nickel lithium manganate cathode material | |
| CN106025276B (en) | A kind of preparation method and lithium ion battery of carbon coating vanadium trioxide nano material | |
| CN102328952B (en) | Preparation method for spherical lithium titanate material | |
| CN108493458B (en) | High-performance echinoid nickel oxide/nickel cobaltate microsphere lithium oxygen battery positive electrode catalytic material and preparation method thereof | |
| CN102013479A (en) | Method for preparing carbon-encapsulated zirconium-doped lithium titanium as lithium ion battery cathode material | |
| CN110416509A (en) | A kind of lithium ion battery negative material of height ratio capacity and preparation method thereof | |
| CN108493435A (en) | Anode material for lithium-ion batteries Li (Ni0.8Co0.1Mn0.1)1-xYxO2And preparation method | |
| CN115020643A (en) | Biomass-based hard carbon, preparation method thereof and application thereof in sodium-ion battery | |
| CN108598394A (en) | Carbon coating titanium phosphate manganese sodium micron ball and its preparation method and application | |
| CN103367718A (en) | Method for preparing carbon-coated Fe3O4 nanometer microspheres | |
| CN104091941B (en) | A kind of lithium-rich manganese-based Layered Lithium cell positive material and preparation method thereof | |
| CN111933899B (en) | Composite oxide electrode material and preparation method thereof | |
| CN102800858A (en) | Preparation method and purpose for iron oxide-based anode material for lithium ion battery | |
| CN105481004B (en) | A kind of high electric property tin dioxide nanometer tube and preparation method thereof | |
| CN108695507A (en) | A kind of preparation method and applications of the porous cobaltosic oxide nano particle of carbon coating | |
| CN103066285A (en) | Preparation method of negative pole material of lithium ion battery | |
| CN101867036A (en) | Lithium-ion battery cathode material with long service life and high power as well as preparation method thereof | |
| CN105702951A (en) | Multiple-linkage modified lithium-rich manganese-based material and modification method thereof | |
| CN104600283A (en) | Lithium-enriched electrode material as well as preparation method and application thereof | |
| CN101286562A (en) | Preparation method of positive electrode material of lithium ion cell |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181023 |