CN107887581A - Porous graphene coated graphite, preparation and the application on lithium ion battery - Google Patents
Porous graphene coated graphite, preparation and the application on lithium ion battery Download PDFInfo
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- CN107887581A CN107887581A CN201711038173.2A CN201711038173A CN107887581A CN 107887581 A CN107887581 A CN 107887581A CN 201711038173 A CN201711038173 A CN 201711038173A CN 107887581 A CN107887581 A CN 107887581A
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- H—ELECTRICITY
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- 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
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- 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
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- H—ELECTRICITY
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- 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
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H01M4/625—Carbon or graphite
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Abstract
The present invention relates to field of nanocomposite materials, discloses a kind of porous graphene coated graphite nano composite material, preparation method and its application as lithium ion battery negative material.Porous graphene is coated on the surface of graphite in the composite.When for lithium ion battery negative material, high capacity, good high rate performance and cyclical stability are shown.The composite material and preparation method thereof is simple, and raw material resources used is abundant, cost is relatively low, and preparation technology is simple, is easy to mass produce.
Description
Technical field
The invention belongs to nano composite material technical field, and in particular to a kind of porous graphene coated graphite composite wood
Material, preparation method and its application as lithium ion battery negative material.
Background technology
At present, commercialized negative material is mainly graphite material, but because its Capacity Ratio is relatively low, and be not suitable for
Fast charging and discharging, become the main reason for restricting lithium ion battery development.Therefore, development is with higher capacity, more preferable multiplying power
Performance, low cost, long-life and safe and reliable novel anode material are very urgent.
The method of modifying of traditional negative material mainly includes coating modification, oxidation modification, doping vario-property and surface deposition
Metal or metal oxide.Oxidizing process advantage is can to use the air of low cost, but it has the shortcomings that one very big
Exactly oxidation can only occur in the particle surface that air contact arrives, therefore prepared material is it is difficult to ensure that its homogeneity.Doping
Some hetero atoms that modification can be introduced outside carbon atom, coulombic efficiency reduction first can be caused.Surface deposited metal or gold
Although category oxide can improve the cycle performance of electrode, metal ion can greatly be broken in the test process of full battery
The overall performance of bad battery.Coating modification is the unformed charcoal " shell " of one layer of Surface coating in graphite, forms " core-shell structure copolymer " knot
Structure, the shortcomings that can effectively avoiding graphite carbon material.It is possible, firstly, to reduce the irreversible capacity of graphite material;Secondly, can
To improve the electrolyte adaptability of graphite material so that it can be used in the electrolyte that PC is solvent;Finally, can improve
The cyclical stability of graphite material.Therefore, compared with other method of modifying, coating modification is considered as a kind of simple and had
The method of effect.
Traditional cladding presoma mainly includes macromolecule and pitch, Jiao such as phenolic resin, epoxy resin, polyvinyl alcohol
The byproduct of the coals such as charcoal or oil.But the clad formed is generally thicker, it is difficult to strict control.Graphene is due to tool
There are high electrical conductivity, big ratio surface and excellent mechanical performance, be expected to the negative material as lithium ion battery.Porous stone
On the one hand black alkene has the intrinsic very good mechanical properties of common graphite alkene and electric conductivity, on the other hand lacked containing many extra
Fall into, therefore receive much concern.Special loose structure promotes electrolyte when alloing it as lithium ion battery negative material
Infiltration, shorten the diffusion length of lithium ion, so as to improve chemical property.But graphene can not individually be used as lithium ion again
The negative material of battery, this does not have obvious platform mainly due to it, it is impossible to have a stable voltage output, and cost compared with
It is high.Accordingly, it is desirable to provide porous graphene coated graphite composite, preparation method and its conduct of a kind of advantages with reference to both
The application of lithium ion battery negative material.
The content of the invention
It is an object of the invention to for existing graphite electrode specific capacity it is relatively low the problem of, there is provided a kind of porous graphene
Coated graphite, preparation method and its application as lithium ion battery negative material.
Technical scheme is as follows:
A kind of porous graphene coated graphite nano composite material, including porous graphene and graphite, described porous stone
Black alkene is coated on the surface of graphite.
A kind of preparation method of porous graphene coated graphite nano composite material as claimed in claim 1, its feature
It is in turn include the following steps:
Step 1. prepares graphene dispersing solution, is 1 by the mass ratio of graphene and metal salt:100~1:0.01 to graphite
Metal salt is added in alkene dispersion liquid and obtains mixed solution;
Then mixed solution that step 2. obtains step 1, which is placed in ultrasonic machine, be ultrasonically treated 0 minute to 1 hour,
Then through magnetic stirrer 1-24 hours, then graphene metal salt mixture is obtained after freezing;By obtained graphene gold
Category salt mixture is placed in inert atmosphere, is in 100-1000 DEG C of progress charing process, the sample after being carbonized, reaction time
0 minute to 10 hours;Then the sample after charing being handled with acid solution again, the concentration of hydrochloric acid is 0.01-10mol/L,
Processing time is 30 minutes to 8 hours;It is lyophilized to obtain porous graphene powder after neutrality is washed with deionized again;
Then porous graphene powder that step 3. obtains step 2 is 1 according to mass ratio with graphite:100~1:0.01
Solid phase mixing;Mixed material is placed in inert atmosphere again, charing process, reaction time 0 are carried out at 100-1000 DEG C
Minute was by 10 hours, you can obtains porous graphene coated graphite nano composite material.
The mass ratio of graphene and metal salt is 1 in step 1:10~1:0.1.
Graphene oxide, redox graphene or the machinery stripping that graphene described in step 1 is prepared for chemical method
The graphene prepared from method.
Metal salt described in step 1 is transition metal sulfate, transition metal nitrate, transition metal chloride or mistake
Cross metal acetate.
The transition metal sulfate is ferric sulfate, cobaltous sulfate, nickel sulfate, copper sulphate or manganese sulfate;The transition metal
Nitrate is ferric nitrate, cobalt nitrate, nickel nitrate, copper nitrate or manganese nitrate;The transition metal chloride is iron chloride, chlorination
Cobalt, nickel chloride, copper chloride or manganese chloride;The transition metal acetate is ferric acetate, cobalt acetate, nickel acetate, copper acetate or second
Sour manganese.
The methods of solid phase mixing method described in step 3 can use grinding or ball milling.
Porous graphene powder and graphite quality ratio are 1 in step 3:10~1:0.1.
The porous graphene coated graphite nano composite material being prepared is as lithium ion battery negative material.
A kind of lithium ion battery, the porous graphene coated graphite nanometer that negative material employs described in claim 1 are answered
Condensation material.
The beneficial effects of the present invention are:
1. the porous graphene coated graphite nano composite material prepared by the present invention mainly has following characteristics:(1) it is porous
The loose structure of graphene can shorten the diffusion path of lithium ion, there is provided more storage lithium avtive spots;(2) porous graphene
Graphite surface is coated on, therefore can effectively improve the cycle performance of graphite.
2. preparation technology provided by the invention, which need to only pass through simple mixing and carbonization process, can obtain porous graphene
Coated graphite electrode material.Raw material resources used in the present invention enriches, cost is relatively low, and preparation technology is simple, is easy to advise greatly
The production of mould.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of the porous graphene coated graphite nano composite material of the present invention;
Fig. 2 is the cycle performance curve of the porous graphene coated graphite nano composite material of the present invention.
Embodiment
Below in conjunction with the accompanying drawings and specific embodiment is described in further detail to the present invention.
Embodiment 1
Present embodiments provide a kind of porous graphene coated graphite nano composite material, including porous graphene and stone
Ink, described porous graphene are coated on the surface of graphite.Described graphite can be native graphite or Delanium.
The present embodiment additionally provides a kind of preparation method of above-mentioned porous graphene coated graphite nano composite material, successively
Comprise the following steps:
Graphene powder is added to the water by step 1. is prepared into graphene dispersing solution, by graphene and the mass ratio of metal salt
For 1:100~1:0.01 adds metal salt into graphene dispersing solution obtains mixed solution.The mass ratio of graphene and metal salt
Preferably 1:10~1:0.1.
Described graphene is prepared by graphene oxide, redox graphene or mechanical stripping method prepared by chemical method
Graphene.
Described metal salt is transition metal sulfate, transition metal nitrate, transition metal chloride or transition metal
Acetate.The transition metal sulfate is ferric sulfate, cobaltous sulfate, nickel sulfate, copper sulphate or manganese sulfate;The transition metal nitre
Hydrochlorate is ferric nitrate, cobalt nitrate, nickel nitrate, copper nitrate or manganese nitrate;The transition metal chloride be iron chloride, cobalt chloride,
Nickel chloride, copper chloride or manganese chloride;The transition metal acetate is ferric acetate, cobalt acetate, nickel acetate, copper acetate or acetic acid
Manganese.
Then mixed solution that step 2. obtains step 1, which is placed in ultrasonic machine, be ultrasonically treated 0 minute to 1 hour,
Then through magnetic stirrer 1-24 hours, reuse after freeze dryer freezes and obtain graphene metal salt mixture;
Obtained graphene metal salt mixture is placed in inert atmosphere, charing process is carried out at 100-1000 DEG C, obtains
Sample after to charing, reaction time are 0 minute to 10 hours;
Then the sample after charing is handled with hydrochloric acid again, the concentration of hydrochloric acid is 0.01-10M, processing time 30
Minute was by 8 hours;
After neutrality is washed with deionized again, porous graphene powder is obtained after lyophilized;
Then porous graphene powder that step 3. obtains step 2 is 1 according to mass ratio with graphite:100~1:0.01
Solid phase mixing;Mixed material is placed in inert atmosphere again, charing process, reaction time 0 are carried out at 100-1000 DEG C
Minute was by 10 hours, you can obtains porous graphene coated graphite nano composite material.Described solid phase mixing method can adopt
The methods of with grinding or ball milling.Porous graphene powder and graphite quality ratio preferably 1:10~1:0.1.
The present embodiment additionally provides a kind of lithium ion battery, and its negative material employs above-mentioned porous graphene coated graphite
Nano composite material.
Compared with prior art, the technical scheme of the present embodiment has advantages below:
1. the porous graphene coated graphite nano composite material prepared by the present invention mainly has following characteristics:(1) it is porous
The loose structure of graphene can shorten the diffusion path of lithium ion, there is provided more storage lithium avtive spots;(2) porous graphene
Graphite surface is coated on, therefore can effectively improve the cycle performance of graphite.
2. preparation technology provided by the invention, which need to only pass through simple mixing and carbonization process, can obtain porous graphene
Coated graphite electrode material.Raw material resources used in the present invention enriches, cost is relatively low, and preparation technology is simple, is easy to advise greatly
The production of mould.
Embodiment 2
It is 1 in mass ratio:1 adds 1g ferric nitrates into 1g graphene oxide solutions forms mixed solution.Then put
Ultrasound 30 minutes in ultrasonic machine, stirred on magnetic stirring apparatus 10 hours, graphene is obtained after then being freezed using freeze dryer
Metal salt mixture, the graphene metal salt mixture after freezing are placed in inert atmosphere, and charing process are carried out at 800 DEG C,
Reaction time is 3 hours, processing 2 hours is then carried out to the sample after charing with 0.1M hydrochloric acid again, then be washed with deionized water
It is lyophilized to can obtain porous graphene powder after washing neutrality.Then it is according to mass ratio with graphite by porous graphene powder
1:10 solid phase mixings, mixed material is placed in inert atmosphere, carries out charing process 1h at 1000 DEG C, you can obtain porous
Graphene coated graphite nanometer composite material.As the scanning electron microscope analysis of accompanying drawing 1 show prepared porous graphene bag
Cover the surface that porous graphene in graphite nanometer composite material is coated on graphite.As the electrochemical property test result of accompanying drawing 2 shows,
The composite material is under 0.5C current densities after 90 circulations, and capacity is still up to 353mAh/g.
Embodiment 3
Porous graphene preparation method is changed to 1 with embodiment 2, porous graphene powder with graphite quality ratio:5, maintain it
Its condition is constant.Electrochemical property test result shows that the composite material is under 0.5C current densities by 100 circulations
Afterwards, capacity is still up to 362mAh/g.
Embodiment 4
Porous graphene preparation method is changed to 1 with embodiment 2, porous graphene powder with graphite quality ratio:4, maintain it
Its condition is constant.Electrochemical property test result shows that the composite material is under 0.5C current densities by 100 circulations
Afterwards, capacity is still up to 367mAh/g.
Embodiment 5
Porous graphene preparation method is changed to 1 with embodiment 2, porous graphene powder with graphite quality ratio:3, maintain it
Its condition is constant.Electrochemical property test result shows that the composite material is under 0.5C current densities by 100 circulations
Afterwards, capacity is still up to 373mAh/g.
Embodiment 6
Porous graphene preparation method is changed to 1 with embodiment 2, porous graphene powder with graphite quality ratio:2, maintain it
Its condition is constant.Electrochemical property test result shows that the composite material is under 0.5C current densities by 100 circulations
Afterwards, capacity is still up to 381mAh/g.
Obviously, those skilled in the art can carry out the essence of various changes and modification without departing from the present invention to the present invention
God and scope.It is if these modifications and variations belong within the scope of the claims in the present invention and its equivalent technologies, then of the invention
It is also intended to comprising including these changes and modification.
Claims (10)
- A kind of 1. porous graphene coated graphite nano composite material, it is characterised in that:It is described including porous graphene and graphite Porous graphene be coated on the surface of graphite.
- 2. a kind of preparation method of porous graphene coated graphite nano composite material as claimed in claim 1, its feature exist In in turn including the following steps:Step 1. prepares graphene dispersing solution, is 1 by the mass ratio of graphene and metal salt:100~1:0.01 divides to graphene Metal salt is added in dispersion liquid and obtains mixed solution;Then mixed solution that step 2. obtains step 1, which is placed in ultrasonic machine, carries out supersound process 0 minute to 1 hour, then Through magnetic stirrer 1-24 hours, then graphene metal salt mixture is obtained after freezing;Obtained graphene metal salt mixture is placed in inert atmosphere, charing process is carried out at 100-1000 DEG C, obtains charcoal Sample after change, reaction time are 0 minute to 10 hours;Then the sample after charing is handled with acid solution again, the concentration of hydrochloric acid is 0.01-10mol/L, and processing time is 30 minutes to 8 hours;It is lyophilized to obtain porous graphene powder after neutrality is washed with deionized again;Then porous graphene powder that step 3. obtains step 2 is 1 according to mass ratio with graphite:100~1:0.01 solid phase Mixing;Mixed material is placed in inert atmosphere again, charing process is carried out at 100-1000 DEG C, the reaction time is 0 minute By 10 hours, you can obtain porous graphene coated graphite nano composite material.
- 3. a kind of preparation method of porous graphene coated graphite nano composite material as claimed in claim 2, its feature exist In:The mass ratio of graphene and metal salt is 1 in the step 1:10~1:0.1.
- 4. a kind of preparation method of porous graphene coated graphite nano composite material as claimed in claim 2 or claim 3, its feature It is:Graphene described in step 1 is graphene oxide, redox graphene or mechanical stripping method prepared by chemical method The graphene of preparation.
- 5. a kind of preparation method of porous graphene coated graphite nano composite material as claimed in claim 2 or claim 3, its feature It is:Metal salt described in step 1 is transition metal sulfate, transition metal nitrate, transition metal chloride or transition Metal acetate.
- 6. a kind of preparation method of porous graphene coated graphite nano composite material as claimed in claim 5, its feature exist In:The transition metal sulfate is ferric sulfate, cobaltous sulfate, nickel sulfate, copper sulphate or manganese sulfate;The transition metal nitrate For ferric nitrate, cobalt nitrate, nickel nitrate, copper nitrate or manganese nitrate;The transition metal chloride is iron chloride, cobalt chloride, chlorination Nickel, copper chloride or manganese chloride;The transition metal acetate is ferric acetate, cobalt acetate, nickel acetate, copper acetate or manganese acetate.
- 7. a kind of preparation method of porous graphene coated graphite nano composite material as claimed in claim 2 or claim 3, its feature It is:The methods of solid phase mixing method described in step 3 can use grinding or ball milling.
- 8. a kind of preparation method of porous graphene coated graphite nano composite material as claimed in claim 2 or claim 3, its feature It is:Porous graphene powder and graphite quality ratio are 1 in step 3:10~1:0.1.
- 9. a kind of preparation method of porous graphene coated graphite nano composite material as claimed in claim 2 or claim 3, its feature It is:The porous graphene coated graphite nano composite material being prepared is as lithium ion battery negative material.
- A kind of 10. lithium ion battery, it is characterised in that:Negative material employs the porous graphene cladding described in claim 1 Graphite nanometer composite material.
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CN109411723A (en) * | 2018-10-16 | 2019-03-01 | 上海应用技术大学 | A kind of preparation method of graphene/graphite lithium ion battery negative electrode material |
CN109585821A (en) * | 2018-11-23 | 2019-04-05 | 四川大学 | Graphite composite material, preparation method, application and negative electrode of lithium ion battery |
CN110085820A (en) * | 2019-04-17 | 2019-08-02 | 中国航发北京航空材料研究院 | A kind of preparation method of the porous graphene silicium cathode material based on supercritical fluid auxiliary |
CN110112384A (en) * | 2019-04-17 | 2019-08-09 | 中国航发北京航空材料研究院 | A kind of preparation method of porous graphene silicium cathode material |
CN110627034A (en) * | 2019-07-31 | 2019-12-31 | 宁波中车新能源科技有限公司 | Preparation method of dual-functional energy-storage porous carbon-coated graphite composite material |
CN111807353A (en) * | 2020-07-17 | 2020-10-23 | 北京石墨烯研究院 | Porous graphene and preparation method and application thereof |
CN113161545A (en) * | 2021-05-18 | 2021-07-23 | 芜湖天弋能源科技有限公司 | Graphene and graphite composite material, preparation method and application of graphene and graphite composite material as lithium ion battery negative electrode material |
CN113871590A (en) * | 2021-09-16 | 2021-12-31 | 广东凯金新能源科技股份有限公司 | Layered porous graphite negative electrode material and preparation method thereof |
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CN109585821A (en) * | 2018-11-23 | 2019-04-05 | 四川大学 | Graphite composite material, preparation method, application and negative electrode of lithium ion battery |
CN110085820A (en) * | 2019-04-17 | 2019-08-02 | 中国航发北京航空材料研究院 | A kind of preparation method of the porous graphene silicium cathode material based on supercritical fluid auxiliary |
CN110112384A (en) * | 2019-04-17 | 2019-08-09 | 中国航发北京航空材料研究院 | A kind of preparation method of porous graphene silicium cathode material |
CN110627034A (en) * | 2019-07-31 | 2019-12-31 | 宁波中车新能源科技有限公司 | Preparation method of dual-functional energy-storage porous carbon-coated graphite composite material |
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JP2023515605A (en) * | 2020-03-13 | 2023-04-13 | エルジー エナジー ソリューション リミテッド | Negative electrode active material, manufacturing method thereof, and lithium secondary battery comprising said negative electrode active material |
CN111807353A (en) * | 2020-07-17 | 2020-10-23 | 北京石墨烯研究院 | Porous graphene and preparation method and application thereof |
CN114373897A (en) * | 2020-10-14 | 2022-04-19 | 山东欧铂新材料有限公司 | Porous graphene/artificial graphite composite material, preparation method thereof and lithium ion battery |
CN114477155A (en) * | 2020-10-27 | 2022-05-13 | 中国科学院大连化学物理研究所 | Porous graphene/lamellar graphene composite material and preparation method and application thereof |
CN114477155B (en) * | 2020-10-27 | 2023-11-10 | 中国科学院大连化学物理研究所 | Porous graphene/lamellar graphene composite material and preparation method and application thereof |
CN113161545B (en) * | 2021-05-18 | 2022-06-24 | 芜湖天弋能源科技有限公司 | Graphene and graphite composite material, preparation method and application of graphene and graphite composite material as lithium ion battery negative electrode material |
CN113161545A (en) * | 2021-05-18 | 2021-07-23 | 芜湖天弋能源科技有限公司 | Graphene and graphite composite material, preparation method and application of graphene and graphite composite material as lithium ion battery negative electrode material |
CN113871590A (en) * | 2021-09-16 | 2021-12-31 | 广东凯金新能源科技股份有限公司 | Layered porous graphite negative electrode material and preparation method thereof |
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