CN110311099A - A kind of carbon coating oxide electrode material and preparation method thereof - Google Patents
A kind of carbon coating oxide electrode material and preparation method thereof Download PDFInfo
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- CN110311099A CN110311099A CN201810248983.9A CN201810248983A CN110311099A CN 110311099 A CN110311099 A CN 110311099A CN 201810248983 A CN201810248983 A CN 201810248983A CN 110311099 A CN110311099 A CN 110311099A
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- electrode material
- oxide electrode
- oxide
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- carbon
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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
- H01M4/366—Composites as layered products
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of oxide electrode material/C composites and preparation method thereof, the composite material is made of the oxide coated electrode material of carbon-coating, its synthetic method is that have the carbon coating oxide electrode material of excellent properties by Solid phase synthesis using carbon source and oxide as raw material.The preparation method is evenly coated, simple and easy, and yield is higher, and cost is relatively low.In this way, the electric conductivity of oxide electrode material has apparent increase, environmental stability is also significantly improved.
Description
Technical field
The present invention relates to a kind of battery electrode material, in particular to a kind of carbon coating oxide electrode material and synthesis in solid state
Oxide electrode material/C composite method, belongs to materials synthesis and electrochemical field.
Background technique
Shortage of resources, environmental disruption are two stern challenges that the mankind are faced 21 century, with holding for world economy
Supervention exhibition can increasingly be reduced by human development and the resource utilized, during ecological environment also runs down.So people are increasingly
Pay close attention to the development and utilization of new energy.The new energy and new energy materials for exploring cleanliness without any pollution have become social sustainable development
The grand strategy of exhibition selects.The energy such as solar energy, wind energy, nuclear energy are gradually developed and used, in order to charge and discharge development and utilization
These new energy are also badly in need of developing matched high-performance energy storage device.
Currently, metal oxide with its with high capacity, low cost, be suitble to commercialized development, obtained the extensive of people
Concern.But metal oxide electrode material is there is also such as in charge and discharge process, volume change is larger, and resistivity compared with
Greatly, it so that battery high rate performance is poor, limits it not and can be carried out good fast charging and discharging.
Summary of the invention
Existing metal oxide electrode material there are aiming at the problem that, the purpose of the present invention is to provide a kind of electric conductivity is good
Good carbon coating oxide electrode material.
Another object of the present invention is to provide a kind of simple and easy, higher and lower-cost synthetic methods of yield.
To realize the above-mentioned technical purpose, the present invention provides a kind of carbon coating oxide electrode materials and preparation method thereof.
Carbon coating oxide electrode material is combined by carbon coating oxide electrode material.Technical solution of the present invention passes through will be by oxygen
It after compound electrode material and carbon source ball milling mixing, is placed in protective atmosphere, is sintered to get composite material is arrived.
Preferred scheme, oxide electrode material include the oxygen of the oxide of manganese, titanyl compound, the oxide of iron, nickel
The oxide wherein at least one of compound, the oxide of cobalt, the oxide of molybdenum and vanadium.
More preferably scheme, oxide electrode material have nanometer or micrometer structure.
More preferably scheme is placed in protective atmosphere, is warming up to after oxide electrode material and carbon source ball milling mixing
600~1500 DEG C are sintered to get composite material is arrived.
Preferred scheme, the dosage of the carbon source be generate oxide electrode material/C composite quality 3%~
100%.
Preferred scheme, the carbon source include glucose, starch, sucrose, citric acid, polyvinyl alcohol, polyacrylonitrile, stone
At least one of ink, conductive black, active carbon, carbon nanotube, carbon fiber, graphene.
Preferred scheme, the condition of the ball milling are as follows: ball material mass ratio is 8~50:1；Engine speed be 500~
1600r/min, Ball-milling Time are 1~48h.
Preferred scheme, the ball milling carry out in organic solvent medium, more preferably ethyl alcohol, acetone, isopropylamine, second
Glycol wherein at least one.Organic solvent makes solid have better wetability, ball milling mixing effect is improved, to obtain pure
Spend better product.
Preferred scheme, oxide electrode material and carbon source after ball milling mixing, are placed in 60~120 DEG C of temperature in organic media
Lower drying is spent, it is dry at a temperature of being more preferably placed in 80~100 DEG C.
Preferred scheme, protective atmosphere include nitrogen, argon gas or its mixed gas.In the time that 600~1500 DEG C are sintered
For 1~for 24 hours, heating rate is 2~20 DEG C/min.Preferred scheme, 800~1000 DEG C be sintered time be 1~for 24 hours,
Heating rate is 2~5 DEG C/min.
Preferred scheme, 600~1500 DEG C be sintered time be 1~for 24 hours, heating rate be 2~20 DEG C/min.
Compared with prior art, technical solution of the present invention bring advantageous effects:
Carbon coating oxide electrode material of the invention has good electric conductivity, can reduce in battery charge and discharge process
The volume change of oxide improves battery high rate performance and fast charging and discharging ability.
The present invention synthesizes carbon coating oxide electrode material by simple solid-phase synthesis, and preparation method cladding is equal
Even, simple and easy, yield is higher, and cost is relatively low.
Detailed description of the invention
Fig. 1 is oxide electrode material/C scanning electron microscope (SEM) photograph prepared by the embodiment of the present invention 1.
Fig. 2 is oxide electrode material/C scanning electron microscope (SEM) photograph prepared by the embodiment of the present invention 2.
Fig. 3 is oxide electrode material/C scanning electron microscope (SEM) photograph prepared by the embodiment of the present invention 3.
Fig. 4 is oxide electrode material/C scanning electron microscope (SEM) photograph prepared by the embodiment of the present invention 4.
Fig. 5 is oxide electrode material/C scanning electron microscope (SEM) photograph prepared by the embodiment of the present invention 5.
Specific embodiment
The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments, but protection of the invention
Range is not limited thereto.
Embodiment 1
Manganese dioxide and conductive black are mixed with the mass ratio of 9:1, ethyl alcohol is added as organic solvent, ball material mass ratio
It is dry at a temperature of being subsequently placed in 80 DEG C after engine speed 1000r/min, ball milling 5h for 10:1.Resulting material is placed in atmosphere
In furnace, 10h is sintered at 900 DEG C under ar gas environment with the heating rate of 5 DEG C/min, obtains manganese dioxide/C composite.
Manganese dioxide object crystalline substance row after carbon coating is good, and body of material partial size is 50~100nm, and is distributed equal
It is even.(Fig. 1)
Embodiment 2
Manganese dioxide and 1500 mesh expanded graphite powder are mixed with the mass ratio of 8:1, isopropylamine are added as organic solvent,
Ball material mass ratio is 10:1, dry at a temperature of being subsequently placed in 80 DEG C after engine speed 700r/min, ball milling 10h.By gains
Material is placed in atmosphere furnace, is sintered 10h at 1000 DEG C under ar gas environment with the heating rate of 5 DEG C/min, is obtained manganese dioxide/C
Composite material.
Manganese dioxide object crystalline substance row after carbon coating is good, and main body partial size is 50~100nm and 0.5~0.8 μm,
And distribution is relatively uniform.(Fig. 2)
Embodiment 3
Manganese dioxide and 5000 mesh expanded graphite powder are mixed with the mass ratio of 9:1, acetone is added as organic solvent, ball
Material mass ratio is 10:1, dry at a temperature of being subsequently placed in 80 DEG C after engine speed 500r/min, ball milling 2h.By resulting material
It is placed in atmosphere furnace, 10h is sintered at 1000 DEG C under ar gas environment with the heating rate of 5 DEG C/min, it is multiple to obtain manganese dioxide/C
Condensation material.
Manganese dioxide object crystalline substance row after carbon coating is good, and main body partial size is 50~100nm, it is seen that expanded graphite
Lamella, and be distributed it is relatively uniform.(Fig. 3)
Embodiment 4
Manganese dioxide and 8000 mesh expanded graphite powder are mixed with the mass ratio of 7:1, ethyl alcohol is added as organic solvent, ball
Material mass ratio is 10:1, dry at a temperature of being subsequently placed in 80 DEG C after engine speed 1000r/min, ball milling 2h.By resulting material
It is placed in atmosphere furnace, 5h is sintered at 900 DEG C under ar gas environment with the heating rate of 5 DEG C/min, it is compound to obtain manganese dioxide/C
Material.
Manganese dioxide object crystalline substance row after carbon coating is good, and main body partial size is 50~100nm and 0.3~0.8 μm,
And distribution is relatively uniform.(Fig. 4)
Embodiment 5
Titanium dioxide and conductive carbon black are mixed with the mass ratio of 8:1, ethyl alcohol is added as organic solvent, ball material mass ratio
It is dry at a temperature of being subsequently placed in 80 DEG C after engine speed 800r/min, ball milling 5h for 10:1.Resulting material is placed in atmosphere
In furnace, 5h is sintered at 900 DEG C under ar gas environment with the heating rate of 5 DEG C/min, obtains titanium dioxide/C composite.
Titania oxide crystalline substance row after carbon coating is good, and main body partial size is about 100nm and 0.5~2 μm, and point
Cloth is relatively uniform.(Fig. 5)
Embodiment of above is only for interpreting the claims, and protection scope of the present invention is not limited to specification.
Anyone skilled in the art within the technical scope of the present disclosure, the variation that can readily occur in or replaces
It changes, is included within the scope of the present invention.
Claims (10)
1. a kind of carbon coating oxide electrode material and preparation method thereof, it is characterised in that: by carbon coating oxide electrode material
It is combined.
2. carbon coating oxide electrode material according to claim 1, it is characterised in that: oxide electrode material includes manganese
Oxide, titanyl compound, the oxide of iron, the oxide of nickel, the oxide of cobalt, the oxide of molybdenum and vanadium oxide its
At least one of.
3. oxide electrode material according to claim 1 or 2 or 3, it is characterised in that: oxide electrode material, which has, to be received
Rice or micrometer structure.
4. the preparation method of oxide electrode material/C composite according to claim 1 or 2, it is characterised in that:
It after oxide electrode material and carbon source ball milling mixing, is placed in protective atmosphere, is warming up to 600~1500 DEG C of sintering, i.e.,
Obtain composite material.
5. the preparation method of oxide electrode material/C composite according to claim 4, it is characterised in that: the carbon
The dosage in source is the oxide electrode material/C composite quality 3%~100% generated.
6. the preparation method of oxide anode/C composite according to claim 4 or 5, it is characterised in that: described
Carbon source includes glucose, starch, sucrose, citric acid, polyvinyl alcohol, polyacrylonitrile, graphite, conductive black, active carbon, carbon nanometer
At least one of pipe, carbon fiber, graphene.
7. the preparation method of oxide electrode material/C composite according to any one of claim 4 to 6, feature exist
In: the condition of the ball milling are as follows: ball material mass ratio is 8~50:1；Engine speed is 500~1600r/min, Ball-milling Time 1
~48h.
8. the preparation method of oxide electrode material/C composite according to claim 7, it is characterised in that: described
Ball milling carries out in organic solvent medium.
9. oxide electrode material/C composite preparation method according to claim 4~6,8, it is characterised in that:
Oxide electrode material and carbon source after ball milling mixing, are dried in organic media at a temperature of being placed in 60~120 DEG C.
10. oxide electrode material/C composite preparation method according to claim 4~6,8, it is characterised in that:
Protective atmosphere includes nitrogen, argon gas or its mixed gas；600~1500 DEG C be sintered time be 1~for 24 hours, heating rate 2
~20 DEG C/min.
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| CN201810248983.9A CN110311099A (en) | 2018-03-25 | 2018-03-25 | A kind of carbon coating oxide electrode material and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104269535A (en) * | 2014-09-15 | 2015-01-07 | 南京工业大学 | Preparation method of carbon-coated metal oxide-graphene composite electrode material |
| CN104485456A (en) * | 2014-11-20 | 2015-04-01 | 刘剑洪 | Method for preparing carbon-coated manganous oxide and carbon-coated manganous oxide |
| CN105428619A (en) * | 2015-11-12 | 2016-03-23 | 南阳师范学院 | Preparation method of high-performance Ti2Nb10O29/C composite electrode material |
-
2018
- 2018-03-25 CN CN201810248983.9A patent/CN110311099A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104269535A (en) * | 2014-09-15 | 2015-01-07 | 南京工业大学 | Preparation method of carbon-coated metal oxide-graphene composite electrode material |
| CN104485456A (en) * | 2014-11-20 | 2015-04-01 | 刘剑洪 | Method for preparing carbon-coated manganous oxide and carbon-coated manganous oxide |
| CN105428619A (en) * | 2015-11-12 | 2016-03-23 | 南阳师范学院 | Preparation method of high-performance Ti2Nb10O29/C composite electrode material |
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