CN107768648A - A kind of preparation method of new amorphous carbon coated graphite material - Google Patents
A kind of preparation method of new amorphous carbon coated graphite material Download PDFInfo
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- CN107768648A CN107768648A CN201711001635.3A CN201711001635A CN107768648A CN 107768648 A CN107768648 A CN 107768648A CN 201711001635 A CN201711001635 A CN 201711001635A CN 107768648 A CN107768648 A CN 107768648A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a kind of preparation method of new amorphous carbon coated graphite material, comprise the following steps：S01：Graphite material is put into quartziferous tube furnace, is then passed through protective gas into quartziferous tube furnace, the temperature in quartziferous tube furnace is risen into specified reaction temperature；S02：After the temperature in quartziferous tube furnace rises to specified reaction temperature, reaction medium is continually fed into quartziferous tube furnace, after reacting certain time, stopping is passed through reaction medium, then cools, and finally can obtain new amorphous carbon coated graphite material.The beneficial effects of the invention are as follows：Raw material sources are extensive and cheap and easy to get, easy to operate, and industrialized level is high, and properties of product are stable, possess good chemical property index.
Description
Technical field
The present invention relates to the preparing technical field of coated graphite material, more particularly to a kind of new amorphous carbon coated graphite
The preparation method of material.
Background technology
With the development of pure electric automobile, lithium ion battery is increasingly taken seriously.How battery safe, fast is realized
Speed, the discharge and recharge of long-life, turn into the target of lithium battery development of future generation.Current positive electrode species tends towards stability, and development is empty
Between less, how effectively to improve negative material chemical property, the direction sign that will develop as lithium ion battery, native graphite
It is the most important negative material of lithium ion battery, therefore the modification to native graphite is lifting lithium ion battery chemical property
Important channel.
2002, Tsing-Hua University Shen ten thousand was kind in Chinese patent 02125715.9, using spray drying, native graphite is thin
Powder and organic polymer suspension, balling-up is granulated, then through carbonization treatment, obtaining one kind can be containing propene carbonate (PC) electrolyte
The carbon coated graphite microparticles used；2016, Shenzhen Bei Terui new energy materialses limited company was in Chinese patent
In 201610626244.X, mixed using pitch with native graphite, graphite surface and internal void are coated into asphalt material, then pass through
Carbonization treatment is crossed, has obtained a kind of long circulating, low bulk, the graphite cathode material of densification.As can be seen here, by natural stone
One layer of new carbon structure is coated in ink, its chemical property can be significantly improved.Clad is analysed in depth, it can be found that
It is mainly amorphous carbon material.
Traditional cladding, it is this to coat the cladding for being merely resting on surface mainly using the means of material covering material,
Material internal duct can not be reached, therefore there is certain limitation for the modification for material.
The content of the invention
The technical problems to be solved by the invention are for existing electrode slice flexibility degree is high, cladding degree is not high
A kind of defect, there is provided preparation method of new amorphous carbon coated graphite material.
The technical scheme that the present invention solves above-mentioned technical problem is as follows：A kind of system of new amorphous carbon coated graphite material
Preparation Method, comprise the following steps：
S01：Graphite material is put into quartziferous tube furnace, protective gas is then passed through into quartziferous tube furnace, will
Temperature in quartziferous tube furnace rises to specified reaction temperature；
S02：After the temperature in quartziferous tube furnace rises to specified reaction temperature, persistently lead into quartziferous tube furnace
Enter reaction medium, after reacting certain time, stopping is passed through reaction medium, then cools, and finally can obtain new amorphous carbon
Coated graphite material.
On the basis of above-mentioned technical proposal, the present invention can also do following improvement.
Further：In the step S01, the protective gas is nitrogen, hydrogen or argon gas.
The above-mentioned further beneficial effect of scheme is：Make graphite material and reaction medium anti-under anaerobic or hypoxia condition
Should, prevent the surface of graphite material from occurring to aoxidize and decarburization.
Further：In the step S01, the reaction temperature specified is 700 DEG C to 1200 DEG C.
Further：In the step S02, the reaction time of reaction medium and the graphite material in the step S01 is
0.2h to 24h.
It is above-mentioned enter two step schemes beneficial effect be：Reaction medium is set fully to contact with graphite material and fully react.
Further：In the step S02, the reaction medium is the gas phase reaction medium that can be reacted with carbon.
The above-mentioned further beneficial effect of scheme is：Gaseous substance penetrating power is strong, can penetrate into inside graphite material
In microcellular structure, so as to have the function that to improve graphite material internal structure.
Further：In the step S02, the reaction medium is carbon dioxide.
Further：When reaction medium is carbon dioxide, the reaction temperature specified in the step S01 is 900 DEG C
To 1200 DEG C.
It is above-mentioned enter two step schemes beneficial effect be：Reaction medium carbon dioxide is cheap and easy to get, by pyroreaction, by stone
Ink material corrodes into amorphous structure, and production cost is low, and the technological process of production is simple to operation.
Further：In the step S02, the reaction medium is vapor.
Further：When reaction medium is vapor, the reaction temperature specified in the step S01 for 700 DEG C extremely
1200℃。
It is above-mentioned enter two step schemes beneficial effect be：Reaction medium vapor is cheap and easy to get, by pyroreaction, by graphite
Material corrosion is into amorphous structure, and production cost is low, and the technological process of production is simple to operation.
Further：Graphite material in the step S01 is native graphite, hard carbon, carbonaceous mesophase spherules, biomass carbon,
The carbon material product such as Delanium.
The beneficial effects of the invention are as follows：The present invention utilizes penetrating power strong gas phase reaction medium (water vapour or titanium dioxide
Carbon) with the pyroreaction characteristic of carbon material, carbon material is corroded, prepares the decrystallized carbon material structure in top layer, this structure
There is important application value on negative electrode of lithium ion battery, both overcome the formation of carbon negative pole material surface SE I films to battery
The irreversible capacity loss brought, it is embedding existing altogether to turn avoid the solvation that battery occurs in propene carbonate (PC) electrolyte
As；The present invention changes tradition with the theory of material covering material, using reaction equation corrosion principle, by carbon material and uncrystalline layer
It is perfectly combined, greatly improves its electrochemical properties, while gas phase reaction medium is cheap and easy to get, saves raw material, reduces cost,
Simplify the technological process of production.
Brief description of the drawings
Fig. 1 is to prepare native graphite amorphisation schematic diagram in the embodiment of the present invention.
Embodiment
The principle and feature of the present invention are described below in conjunction with accompanying drawing, the given examples are served only to explain the present invention, and
It is non-to be used to limit the scope of the present invention.
A kind of preparation method of new amorphous carbon coated graphite material, it comprises the following steps：
S01：Graphite material is put into quartziferous tube furnace, protective gas is then passed through into quartziferous tube furnace, will
Temperature in quartziferous tube furnace rises to specified reaction temperature；
S02：After the temperature in quartziferous tube furnace rises to specified reaction temperature, persistently lead into quartziferous tube furnace
Enter reaction medium, after reacting certain time, stopping is passed through reaction medium, then cools, and finally can obtain new amorphous carbon
Coated graphite material.
Graphite material in the step S01 need to be carried out instead under anaerobic with the reaction medium in the step S02
Should.
Preferably, in the step S01, the protective gas is nitrogen, hydrogen or argon gas.
Preferably, in the step S01, the reaction temperature specified is 700 DEG C to 1200 DEG C.
Preferably, in the step S02, the reaction time of reaction medium and the graphite material in the step S01 is
0.2h to 24h.
Preferably, in the step S02, the reaction medium is the gas phase reaction medium that can be reacted with carbon.
Preferably, in the step S02, the reaction medium is carbon dioxide.
Preferably, when reaction medium is carbon dioxide, the reaction temperature specified in the step S01 is 900 DEG C
To 1200 DEG C.
Preferably, in the step S02, the reaction medium is vapor.
Preferably, when reaction medium is vapor, the reaction temperature specified in the step S01 for 700 DEG C extremely
1200℃。
Preferably, the graphite material in the step S01 be native graphite, hard carbon, carbonaceous mesophase spherules, biomass carbon,
The carbon material product such as Delanium.
When reaction medium is vapor, vapor is passed through quartziferous tube furnace in a manner of being entrained in protective gas
Interior, the reaction of one side graphite material and reaction medium need to be carried out under anaerobic, in the step S01, inherently be needed
Protective gas is passed through, to keep the oxygen-free environment of quartziferous tube furnace；On the other hand, vapor is carried secretly using protective gas,
Water vapor generation device can be saved, saves equipment investment.
Vapor is carried secretly using protective gas, by the way of protective gas is passed through into water column, is made in protective gas as far as possible
Carry saturated steam secretly to enter in the reaction system in quartziferous tube furnace, to shorten the reaction time, save equipment cost and throw
Enter.
Will be specific as experimental condition using different reaction mediums, reaction temperature, reaction time in following each embodiment
Present invention is described.
Embodiment one, a kind of preparation method of new amorphous carbon coated graphite material, it comprises the following steps：
S01：Native graphite is put into quartziferous tube furnace, dry nitrogen is then passed through into quartziferous tube furnace and is made
For protective gas, the temperature in quartziferous tube furnace is risen into specified 750 DEG C of reaction temperature；
S02：After the temperature in quartziferous tube furnace rises to specified 750 DEG C of reaction temperature, into quartziferous tube furnace
The nitrogen of entrainment vapor is continually fed into as reaction medium, after reacting 2h, stops being passed through the nitrogen of entrainment vapor, is passed through dry
Dry nitrogen is cooled, and finally can obtain new amorphous carbon coated graphite material.
Embodiment two, a kind of preparation method of new amorphous carbon coated graphite material, it comprises the following steps：
S01：Native graphite is put into quartziferous tube furnace, dry argon gas is then passed through into quartziferous tube furnace and is made
For protective gas, the temperature in quartziferous tube furnace is risen into specified 1200 DEG C of reaction temperature；
S02：After the temperature in quartziferous tube furnace rises to specified 1200 DEG C of reaction temperature, into quartziferous tube furnace
Dry carbon dioxide is continually fed into as reaction medium, after reacting 10h, stopping is passed through dry carbon dioxide,
It is passed through dry argon gas to be cooled, finally can obtain new amorphous carbon coated graphite material.
Embodiment three, a kind of preparation method of new amorphous carbon coated graphite material, it comprises the following steps：
S01：Native graphite is put into quartziferous tube furnace, dry hydrogen is then passed through into quartziferous tube furnace and is made
For protective gas, the temperature in quartziferous tube furnace is risen into specified 950 DEG C of reaction temperature；
S02：After the temperature in quartziferous tube furnace rises to specified 950 DEG C of reaction temperature, into quartziferous tube furnace
The hydrogen of entrainment saturated steam is continually fed into as reaction medium, after reacting 20h, stops being passed through the hydrogen of entrainment saturated steam
Gas, it is passed through dry hydrogen and is cooled, finally can obtain new amorphous carbon coated graphite material.
Example IV, a kind of preparation method of new amorphous carbon coated graphite material, it comprises the following steps：
S01：Native graphite is put into quartziferous tube furnace, dry nitrogen is then passed through into quartziferous tube furnace and is made
For protective gas, the temperature in quartziferous tube furnace is risen into specified 950 DEG C of reaction temperature；
S02：After the temperature in quartziferous tube furnace rises to specified 950 DEG C of reaction temperature, into quartziferous tube furnace
Dry carbon dioxide is continually fed into as reaction medium, after reacting 24h, stopping is passed through dry carbon dioxide,
It is passed through dry nitrogen to be cooled, finally can obtain new amorphous carbon coated graphite material.
Embodiment five, a kind of preparation method of new amorphous carbon coated graphite material, it comprises the following steps：
S01：Native graphite is put into quartziferous tube furnace, dry nitrogen is then passed through into quartziferous tube furnace and is made
For protective gas, the temperature in quartziferous tube furnace is risen into specified 1050 DEG C of reaction temperature；
S02：After the temperature in quartziferous tube furnace rises to specified 1050 DEG C of reaction temperature, into quartziferous tube furnace
Dry carbon dioxide is continually fed into as reaction medium, after reacting 18h, stopping is passed through dry carbon dioxide,
It is passed through dry nitrogen to be cooled, finally can obtain new amorphous carbon coated graphite material.
As shown in figure 1, after vapor reacts under the high temperature conditions with graphite material, stone is coated except new amorphous carbon is obtained
Outside ink material, reaction product also has hydrogen, carbon monoxide, carbon dioxide；Carbon dioxide is anti-under the high temperature conditions with graphite material
Ying Hou, in addition to new amorphous carbon coated graphite material is obtained, reaction product also has carbon monoxide；Vapor and graphite material
Carbon dioxide is included in reaction product, it can be seen that, carbon dioxide can also be carried out as reaction medium simultaneously with vapor
Same reaction.
Embodiment six, a kind of preparation method of new amorphous carbon coated graphite material, it comprises the following steps：
S01：Native graphite is put into quartziferous tube furnace, dry nitrogen is then passed through into quartziferous tube furnace and is made
For protective gas, the temperature in quartziferous tube furnace is risen into specified 1000 DEG C of reaction temperature；
S02：After the temperature in quartziferous tube furnace rises to specified 1000 DEG C of reaction temperature, into quartziferous tube furnace
The carbon dioxide of entrainment saturated steam is continually fed into as reaction medium, after reacting 16h, stopping is passed through entrainment saturation water
The carbon dioxide of steam, it is passed through dry nitrogen and is cooled, finally can obtain new amorphous carbon coated graphite material
Material.
The foregoing is only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all the present invention spirit and
Within principle, any modification, equivalent substitution and improvements made etc., it should be included in the scope of the protection.
Claims (10)
1. a kind of preparation method of new amorphous carbon coated graphite material, it is characterised in that comprise the following steps：
S01：Graphite material is put into quartziferous tube furnace, is then passed through protective gas into quartziferous tube furnace, by quartz
Temperature in matter tube furnace rises to specified reaction temperature；
S02：After the temperature in quartziferous tube furnace rises to specified reaction temperature, it is continually fed into quartziferous tube furnace anti-
Medium is answered, after reacting certain time, stopping is passed through reaction medium, then cools, and finally can obtain new amorphous carbon cladding
Graphite material.
A kind of 2. preparation method of new amorphous carbon coated graphite material according to claim 1, it is characterised in that：It is described
In step S01, the protective gas is nitrogen, hydrogen or argon gas.
A kind of 3. preparation method of new amorphous carbon coated graphite material according to claim 1, it is characterised in that：It is described
In step S01, the reaction temperature specified is 700 DEG C to 1200 DEG C.
A kind of 4. preparation method of new amorphous carbon coated graphite material according to claim 3, it is characterised in that：It is described
In step S02, the reaction time of reaction medium and the graphite material in the step S01 is 0.2h to 24h.
A kind of 5. preparation method of new amorphous carbon coated graphite material according to claim 1, it is characterised in that：It is described
In step S02, the reaction medium is the gas phase reaction medium that can be reacted with carbon.
A kind of 6. preparation method of new amorphous carbon coated graphite material according to claim 5, it is characterised in that：It is described
In step S02, the reaction medium is carbon dioxide.
A kind of 7. preparation method of new amorphous carbon coated graphite material according to claim 6, it is characterised in that：When anti-
When to answer medium be carbon dioxide, the reaction temperature specified in the step S01 is 900 DEG C to 1200 DEG C.
A kind of 8. preparation method of new amorphous carbon coated graphite material according to claim 5, it is characterised in that：It is described
In step S02, the reaction medium is vapor.
A kind of 9. preparation method of new amorphous carbon coated graphite material according to claim 8, it is characterised in that：When anti-
When to answer medium be vapor, the reaction temperature specified in the step S01 is 700 DEG C to 1200 DEG C.
10. according to a kind of any preparation method of new amorphous carbon coated graphite material of claim 1 to 9, its feature
It is：Graphite material in the step S01 is native graphite, hard carbon, carbonaceous mesophase spherules, biomass carbon, Delanium etc.
Carbon material product.
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Cited By (3)
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| CN114068923A (en) * | 2020-07-30 | 2022-02-18 | 湖南中科星城石墨有限公司 | Modification method of graphite and application of graphite in lithium ion battery |
| CN114068885A (en) * | 2020-07-30 | 2022-02-18 | 湖南中科星城石墨有限公司 | Graphite material with porous carbon layer and preparation method and application thereof |
| CN114068886A (en) * | 2020-07-30 | 2022-02-18 | 湖南中科星城石墨有限公司 | Modified graphite material and preparation method and application thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114068923A (en) * | 2020-07-30 | 2022-02-18 | 湖南中科星城石墨有限公司 | Modification method of graphite and application of graphite in lithium ion battery |
| CN114068885A (en) * | 2020-07-30 | 2022-02-18 | 湖南中科星城石墨有限公司 | Graphite material with porous carbon layer and preparation method and application thereof |
| CN114068886A (en) * | 2020-07-30 | 2022-02-18 | 湖南中科星城石墨有限公司 | Modified graphite material and preparation method and application thereof |
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