CN109037643A - A kind of high capacity high-pressure solid graphite composite material and preparation method thereof - Google Patents
A kind of high capacity high-pressure solid graphite composite material and preparation method thereof Download PDFInfo
- Publication number
- CN109037643A CN109037643A CN201810891875.3A CN201810891875A CN109037643A CN 109037643 A CN109037643 A CN 109037643A CN 201810891875 A CN201810891875 A CN 201810891875A CN 109037643 A CN109037643 A CN 109037643A
- Authority
- CN
- China
- Prior art keywords
- graphite
- composite material
- shell
- high capacity
- preparation
- 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.)
- Granted
Links
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
-
- 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
- H01M4/58—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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to a kind of high capacity high-pressure solid graphite composite materials and preparation method thereof, belong to technical field of lithium ion battery negative.High capacity high-pressure solid graphite composite material of the invention is core-shell structure, and kernel includes graphite and the graphene that is entrained in graphite, and the mass ratio of the graphite and graphene is 100:0.5-1；Shell includes the first shell being coated on outside kernel and the second housing being coated on outside the first shell, and the first shell is lithium metasilicate, and second housing is the carbon-coating of nitrating；The ratio between kernel and the first shell, the thickness of second housing are 100:(5~10): (0.5~2).The greasy property of graphene itself in the kernel of material of the invention can improve the compacted density of material, the good electron conduction of the carbon-coating of the satisfactory electrical conductivity and nitrating of the lithium ion in lithium metasilicate in shell can improve ion under the conditions of the big multiplying power of material and electron transfer rate and first charge discharge efficiency.
Description
Technical field
The present invention relates to a kind of high capacity high-pressure solid graphite composite materials and preparation method thereof, belong to negative electrode of lithium ion battery
Field of material technology.
Background technique
With the raising that market requires electric car course continuation mileage, the energy of lithium ionic cell module and lithium ion battery
Density and rapid charging performance are receive more and more attention.Cathode is the critical material for influencing energy density and rapid charging performance, mesh
Preceding used negative electrode material in the market based on graphite type material, and the specific capacity of graphite type material between 330-360mAh/g it
Between, it is only capable of the charging of support≤2C multiplying power, it is made to be difficult to meet the needs of current and following density to high-energy-density.By to stone
The surface modification of ink material is to improve the common modified method of energy density in the prior art.
Current graphite type material is modified main by material surface cladding and carbonization, such as coats hard carbon, soft carbon, metal oxygen
Compound simultaneously be graphitized modified etc..
To disclose a kind of high capacity long circulating artificial for the Chinese invention patent application that application publication number is CN107039654A
The preparation method of graphite cathode material, mainly pass through after petroleum coke or pitch coke raw material Shape correction with coal tar or petroleum coke
Oil mixing, being then heat-treated, being graphitized and being carbonized is prepared.Its specific capacity is obtained greatly since material has carried out cladding
Amplitude improves, but the first charge discharge efficiency of material and its high rate performance are poor.
Summary of the invention
The purpose of the present invention is to provide a kind of first charge discharge efficiency and the preferable high capacity high-pressure solid graphite of high rate performance are compound
Material.
The object of the invention is also to provide a kind of preparation methods of high capacity high-pressure solid graphite composite material.
To achieve the above object, the technical scheme is that
A kind of high capacity high-pressure solid graphite composite material, is core-shell structure, and kernel is to include graphite and be entrained in graphite
In graphene, the mass ratio of the graphite and graphene is 100:0.5-1；Shell includes the first shell being coated on outside kernel
And it is coated on the second housing outside the first shell, the first shell is lithium metasilicate, and second housing is the carbon-coating of nitrating；Interior nuclear diameter
It is 100:(5~10 with the ratio between the first shell, the thickness of second housing): (0.5~2).
The greasy property of graphene itself in the kernel of material of the invention can improve the compacted density of material, in shell
Lithium metasilicate in lithium ion satisfactory electrical conductivity and nitrating carbon-coating good electron conduction, it is big material can be improved
Ion and electron transfer rate and first charge discharge efficiency under the conditions of multiplying power, material of the invention is high with specific capacity, compacted density is high,
The characteristics such as high rate performance is good.
The mass fraction that nitrogen in the carbon-coating of the nitrating accounts for high capacity high-pressure solid graphite composite material is 2.1-2.5%.
The content of silicon is 3.1-4.2% in high capacity high-pressure solid graphite composite material.
A kind of preparation method of high capacity high-pressure solid graphite composite material, includes the following steps:
1) graphite, graphene oxide, dispersing agent are uniformly mixed in water, by solid at 250-350 DEG C after separation of solid and liquid
Heat preservation 1-6h obtains composite A；
2) lithium metasilicate is deposited on composite A surface, obtains composite material B；
3) composite material B is mixed with nitrogen source compound, be sintered to obtain the final product.
Preparation method of the invention deposits lithium metasilicate in graphite and graphene core surface first, using its lithium metasilicate lithium from
The high characteristic of subconductivity rate improves the conduction velocity of the lithium ion in material, while utilizing the lubrication of the graphene itself in kernel
Effect improves the compacted density and electron conduction of material.Nitrogen source compound is vapor-deposited to form the carbonizable substance of nitrating, avoids interior
Nuclear graphite materials directly reduce the Probability of its side reaction, and the carbonizable substance conduction with higher of nitrating with electrolyte contacts
Property, improve the high rate charge-discharge ability of material.
The dosage of each raw material can be configured as needed in step 1), and the amount of general graphene oxide is less.It is preferred that
, the graphite, dispersing agent, graphene oxide mass ratio be 10-50:1-3:0.05-0.5.The amount of water is unsuitable very few, to protect
It demonstrate,proves graphite and graphene and dispersing agent can be fully dispersed.Preferably, every 10-50g graphite is corresponding uses 500mL water.
The dispersing agent is phyllosilicate.The phyllosilicate of kernel dispersing agent has dispersion performance high graphite material
And the characteristic that layer structure electronic conductivity is high, make high capacity high-pressure solid graphite composite material that there is higher electric conductivity, reduces
Its internal resistance, while the heat dissipation performance of its charge and discharge process can also be enhanced.Specifically, phyllosilicate is by following mass percent
Group is grouped as: 59.5% SiO2, 27.5% MgO, 0.8% Li2O, 2.8% Na2O, 9.4% volatile component.
Graphene oxide solution, i.e., the dispersion being dispersed in water graphene oxide can be used in the graphene oxide
Liquid.In general, using concentration for the graphene oxide solution of 1-10mg/mL.
Being uniformly mixed graphite, graphene oxide, dispersing agent in water in step 1) is to be added to the water graphite, dispersing agent
Graphite presoma mixed liquor is made after mixing, then adds graphene oxide into graphite presoma mixed liquor again.
The mass fraction of graphite and dispersing agent is 2-10% in the graphite presoma mixed liquor.
It is dried in vacuo after being separated by solid-liquid separation in step 1).
Deposition described in step 2) uses gas atomization.
The condition of the gas atomization are as follows: temperature is 1300~1700 DEG C, and aerosolization pressure is 10~50MPa, aerosolization
Gas source be argon gas or nitrogen, time of aerosolization is 10-120min.
Lithium silicate, silicic acid are formd on composite A surface after composite A surface deposits lithium metasilicate in step 2)
Lithium layer with a thickness of 100-500nm.
It is cooled down after composite A surface deposits lithium metasilicate in step 2).The cooling is to be down to room temperature.
The nitrogen source compound is organic compound.The nitrogen source compound be one of aniline, pyrroles, diphenylamines or
Several combinations.
Sintering is 500-800 DEG C of heat preservation 1-12h in step 3).In sintering process, nitrogen source compound gasifies at high temperature, and
It cracks, carbon, the nitrogen free radical generated after cracking is deposited on composite material B surface and forms sedimentary.The ingredient of sedimentary
For the carbon of nitrating.
Detailed description of the invention
Fig. 1 schemes for the SEM of high capacity high-pressure solid graphite composite material obtained in embodiment 1.
Specific embodiment
Technical solution of the present invention is described further combined with specific embodiments below.
Artificial graphite used in following example and comparative example is the model produced by Jiangxi Zi Chen Science and Technology Ltd.
For the artificial graphite of FT-1.
Embodiment 1
The preparation method of the high capacity high-pressure solid graphite composite material of the present embodiment, includes the following steps:
1) 30g artificial graphite, 2g phyllosilicate are added in 500mL distilled water, are uniformly mixing to obtain the total matter of solute
Measure the graphite precursor solution that score is 6.2%；Phyllosilicate consists of the following components in percentage by mass: 59.5%
SiO2, 27.5% MgO, 0.8% Li2O, 2.8% Na2O, 9.4% volatile component.Then molten to graphite presoma
The graphene oxide solution that 50mL concentration is 5mg/mL is added in liquid, stirs evenly, filters, solid is dried in vacuo at 80 DEG C
12h takes out, in 300 DEG C of sintering 3h, obtains composite A.
2) composite A, lithium metasilicate are placed in gas atomization device, are deposited by gas atomization on composite A surface
Lithium metasilicate, cooled to room temperature obtain composite material B；The condition of gas atomization are as follows: temperature is 1500 DEG C, aerosolization pressure
Gas source for 30MPa, aerosolization is argon gas, and the time of aerosolization is 60min.In composite A surface shape after deposition lithium metasilicate
At lithium silicate, lithium silicate with a thickness of 600nm.
3) it after mixing composite material B with aniline, is transferred in tube furnace, keeps the temperature 6h at 700 DEG C, obtain high capacity height
Compacted graphite composite material.
The high capacity high-pressure solid graphite composite material of the present embodiment is core-shell structure, and kernel includes the stone of doped graphene
Ink also contains SiO in the graphite of the doped graphene2、MgO、Li2O、Na2O.Graphite, graphene, SiO2、MgO、Li2O、Na2O
Mass ratio be 100:0.8:4.0:1.8:0.05:0.19；Shell includes the first shell being coated on outside kernel and is coated on the
Second housing outside one shell, the carbon-coating that the first shell is lithium metasilicate, second housing is nitrating.Interior nuclear diameter and the first shell,
The ratio between thickness of second housing is 100:6:1.Wherein, the first shell with a thickness of 600nm, second housing with a thickness of 100nm.
The mass fraction of nitrogen is 2.5% in the high capacity high-pressure solid graphite composite material of the present embodiment.
Embodiment 2
The preparation method of the high capacity high-pressure solid graphite composite material of the present embodiment, includes the following steps:
1) 10g artificial graphite, 1g phyllosilicate are added in 500mL distilled water, are uniformly mixing to obtain the total matter of solute
Measure the graphite precursor solution that score is 2%；Phyllosilicate consists of the following components in percentage by mass: 59.5%
SiO2, 27.5% MgO, 0.8% Li2O, 2.8% Na2O, 9.4% volatile component.Then molten to graphite presoma
The graphene oxide solution that 50mL concentration is 1mg/mL is added in liquid, stirs evenly, filters, solid is dried in vacuo at 80 DEG C
12h takes out, in 250 DEG C of sintering 6h, obtains composite A.
2) composite A, lithium metasilicate are placed in gas atomization device, are deposited by gas atomization on composite A surface
Lithium metasilicate, cooled to room temperature obtain composite material B；The condition of gas atomization are as follows: temperature is 1300 DEG C, aerosolization pressure
Gas source for 10MPa, aerosolization is nitrogen, and the time of aerosolization is 10min.In composite A surface shape after deposition lithium metasilicate
At lithium silicate, lithium silicate with a thickness of 500nm.
3) it after mixing composite material B with pyrroles, is transferred in tube furnace, keeps the temperature 12h at 500 DEG C, obtain high capacity
High-pressure solid graphite composite material.
The high capacity high-pressure solid graphite composite material of the present embodiment is core-shell structure, and kernel includes the stone of doped graphene
Ink also contains SiO in the graphite of the doped graphene2、MgO、Li2O、Na2O.Graphite, graphene, SiO2、MgO、Li2O、Na2O
Mass ratio be 100:0.5:19.8:9.1:0.27:0.93；Shell includes the first shell being coated on outside kernel and is coated on the
Second housing outside one shell, the carbon-coating that the first shell is lithium metasilicate, second housing is nitrating.Interior nuclear diameter and the first shell,
The ratio between thickness of second housing is 100:5:0.5.Wherein, the first shell with a thickness of 500nm, second housing with a thickness of
50nm.The mass fraction of nitrogen is 2.1% in the high capacity high-pressure solid graphite composite material of the present embodiment.
Embodiment 3
The preparation method of the high capacity high-pressure solid graphite composite material of the present embodiment, includes the following steps:
1) 50g artificial graphite, 3g phyllosilicate are added in 500mL distilled water, are uniformly mixing to obtain the total matter of solute
Measure the graphite precursor solution that score is 10%；Phyllosilicate consists of the following components in percentage by mass: 59.5%
SiO2, 27.5% MgO, 0.8% Li2O, 2.8% Na2O, 9.4% volatile component.Then molten to graphite presoma
The graphene oxide solution that 50mL concentration is 10mg/mL is added in liquid, stirs evenly, filters, solid is dried in vacuo at 80 DEG C
12h takes out, in 350 DEG C of sintering 1h, obtains composite A.
2) composite A, lithium metasilicate are placed in gas atomization device, are deposited by gas atomization on composite A surface
Lithium metasilicate, cooled to room temperature obtain composite material B；The condition of gas atomization are as follows: temperature is 1700 DEG C, aerosolization pressure
Gas source for 50MPa, aerosolization is nitrogen, and the time of aerosolization is 120min.In composite A surface shape after deposition lithium metasilicate
At lithium silicate, lithium silicate with a thickness of 1000nm.
3) it after mixing composite material B with diphenylamines, is transferred in tube furnace, keeps the temperature 1h at 800 DEG C, obtain high capacity
High-pressure solid graphite composite material.
The high capacity high-pressure solid graphite composite material of the present embodiment is core-shell structure, and kernel includes the stone of doped graphene
Ink also contains SiO in the graphite of the doped graphene2、MgO、Li2O、Na2O.Graphite, graphene, SiO2、MgO、Li2O、Na2O
Mass ratio be 100:1:11.9:5.5:0.16:0.56；Shell includes the first shell being coated on outside kernel and is coated on first
Second housing outside shell, the carbon-coating that the first shell is lithium metasilicate, second housing is nitrating.Interior nuclear diameter and the first shell, the
The ratio between thickness of two shells is 100:10:2.Wherein, the first shell with a thickness of 1000nm, second housing with a thickness of 200nm.
The mass fraction of nitrogen is 2.1% in the high capacity high-pressure solid graphite composite material of the present embodiment.
Comparative example 1
The preparation method of the graphite composite material of this comparative example includes the following steps:
30g artificial graphite is added in 500mL distilled water, the stone that solute total mass fraction is 6% is uniformly mixing to obtain
Black precursor solution；Then the graphene oxide solution that 50mL concentration is 5mg/mL, stirring are added into graphite precursor solution
Uniformly, it filters, solid is dried in vacuo 12h at 80 DEG C, takes out, in 700 DEG C of sintering 3h, obtains graphite composite material.
Comparative example 2
This comparative example is using artificial graphite as graphite material.
Test example
(1) physicochemical property is tested
1) SEM is tested
High capacity high-pressure solid graphite composite material obtained in embodiment 1 is subjected to SEM test, test result such as Fig. 1 institute
Show.
As can be seen from Figure, high capacity high-pressure solid graphite composite material is presented spherical, and size distribution is uniform, and partial size is situated between
Between (8-15) μm.
2) compacted density is tested
Pole piece compaction density test, the survey of compacted density are carried out to the graphite composite material in embodiment 1-3 and comparative example
Method for testing is the pole piece after the completion of coating to be placed on roll squeezer, and be pressed into design thickness in the case where pressure is the pressure of 20Mpa
Degree, then tests compacted density.
Test result is as shown in table 1.
3) microelement is tested
Microelement test is carried out to the graphite composite material in embodiment 1-3 and comparative example, test method is using ICP member
Plain analysis method.
Test result is as shown in table 1.
The physicochemical property of graphite material in 1 embodiment of table and comparative example
As can be seen from Table 1, the compacted density of composite material produced by the present invention is significantly greater than comparative example, the reason for this is that multiple
Contain a small amount of graphene in condensation material, improves the compacted density of material.Simultaneously because containing lithium metasilicate and nitrating in shell
Carbon material, the material of a small amount of silicon is conducive to improve the gram volume of material, and the substance advantageous of a small amount of nitrogen is in the conduction for improving material
Property.
4) button cell is tested
The graphite material in embodiment 1-3 and comparative example 1-2 is assembled into button cell A1, A2, A3, B1, B2 respectively.Group
Dress method are as follows: add binder, conductive agent and solvent in negative electrode material, be stirred slurrying, be coated on copper foil, by drying
It does, roll obtained negative electrode tab.Binder used is LA132 binder, and conductive agent SP, negative electrode material is respectively embodiment 1-3
With the graphite material in comparative example 1-2, solvent is secondary distilled water.The ratio of each component are as follows: negative electrode material: SP:LA132: two
Secondary distilled water=95g:1g:4g:220mL；Electrolyte is LiPF6/EC+DEC(LiPF6Concentration be 1.2mol/L, EC and DEC body
Product is than being 1:1), metal lithium sheet is to electrode, and diaphragm uses polyethylene (PE), and polypropylene (PP) or poly- second propylene (PEP) are compound
Film.Being assemblied in the glove box for be flushed with hydrogen gas for button cell carries out, and electrochemical property test is in the blue electricity CT2001A type battery in Wuhan
It is carried out on tester, charging/discharging voltage range is 0.005V to 2.0V, charge-discharge magnification 0.1C.Test result is as shown in table 2.
Above-mentioned negative electrode tab is taken simultaneously, tests the imbibition liquid-keeping property of pole piece.
2 embodiment 1-3 of table is compared with the performance of lithium ion battery prepared by the graphite material of comparative example 1
From table 2 it can be seen that the lithium ion battery using graphene composite negative pole obtained by embodiment 1-3 is put for the first time
Capacitance and first charge-discharge efficiency are apparently higher than comparative example, the reason for this is that material core contains the graphite of high electron conduction
Alkene, the nitrating substance high containing conductivity in shell, the gram volume for improving material on the whole plays, to improve it for the first time
Efficiency.Contain lithium ion in lithium metasilicate simultaneously, provides sufficient lithium ion to form SEI in charge and discharge process, further increase
First charge discharge efficiency.
5) soft-package battery is tested
Using the graphite material in embodiment 1-3 and comparative example 1-2 as negative electrode material, cathode pole piece is prepared.With ternary
Material (LiNi1/3Co1/3Mn1/3O2) it is anode, with LiPF6Solution (solvent EC+DEC, volume ratio 1:1, LiPF6Concentration
It is 1.3mol/L) electrolyte, celegard2400 is diaphragm, prepares 2Ah soft-package battery A1, A2, A3 and B1, B2.It surveys later
Try cycle performance, the high rate performance of soft-package battery.
Cycle performance test condition:
Charging and discharging currents 3C/3C, voltage range 3.0-4.2V, cycle-index 300 times.
High rate performance test condition:
Rate of charge: 1C/5C/10C/20C, discharge-rate 1C；Voltage range: 2.5-4.2V.
Test result is shown in Table 3 and table 4.
3 embodiment 1-3 of table is compared with the cycle performance of lithium ion battery prepared by the graphite material of comparative example 1-2
From table 3 it can be seen that the cycle performance for the soft-package battery that graphite material of the invention is prepared is better than comparative example,
Reason is to improve in 3C/3C circulation aspect of performance by the high electric conductivity of kernel graphene and shell nitrogen carbonizable substance
The cycle performance of big multiplying power；It is that sufficient lithium ion is provided in charge and discharge process that outer shell, which contains lithium metasilicate, simultaneously, is further mentioned
Its high cycle performance.
4 multiplying power charging performance contrast table of table
As can be seen from Table 4, the soft-package battery of graphite material of the invention preparation has better constant current ratio, reason
For the material surface in embodiment is coated with silicic acid lithium material, improves the rapid charging performance of material, that is, improves its lithium ion battery
Constant current ratio.
Claims (10)
1. a kind of high capacity high-pressure solid graphite composite material, which is characterized in that be core-shell structure, kernel includes graphite and doping
Graphene in graphite, the graphite, graphene mass ratio be 100:0.5-1；Shell includes be coated on outside kernel
One shell and the second housing being coated on outside the first shell, the first shell are lithium metasilicate, and second housing is the carbon-coating of nitrating；It is interior
The ratio between nuclear diameter and the first shell, the thickness of second housing are 100:(5~10): (0.5~2).
2. a kind of preparation method of high capacity high-pressure solid graphite composite material, which comprises the steps of:
1) graphite, graphene oxide, dispersing agent are uniformly mixed in water, keep the temperature solid at 250-350 DEG C after separation of solid and liquid
1-6h obtains composite A；
2) lithium metasilicate is deposited on composite A surface, obtains composite material B；
3) composite material B is mixed with nitrogen source compound, be sintered to obtain the final product.
3. the preparation method of high capacity high-pressure solid graphite composite material according to claim 2, it is characterised in that: the stone
Ink, dispersing agent, graphene oxide mass ratio be 10-50:1-3:0.05-0.5.
4. the preparation method of high capacity high-pressure solid graphite composite material according to claim 2, it is characterised in that: every 10-
50g graphite is corresponding to use 500mL water.
5. the preparation method of high capacity high-pressure solid graphite composite material according to claim 2, it is characterised in that: described point
Powder is phyllosilicate.
6. the preparation method of high capacity high-pressure solid graphite composite material according to claim 2, it is characterised in that: step 1)
Middle be uniformly mixed graphite, graphene oxide, dispersing agent in water is to be added to the water graphite, dispersing agent to be made after mixing
Then graphite presoma mixed liquor adds graphene oxide into graphite presoma mixed liquor again.
7. the preparation method of high capacity high-pressure solid graphite composite material according to claim 2, it is characterised in that: step 1)
It is dried in vacuo after middle separation of solid and liquid.
8. the preparation method of high capacity high-pressure solid graphite composite material according to claim 2, it is characterised in that: step 2)
Described in deposition use gas atomization.
9. the preparation method of high capacity high-pressure solid graphite composite material according to claim 2, it is characterised in that: the nitrogen
Source compound is the combination of one or more of aniline, pyrroles, diphenylamines.
10. according to the preparation method of high capacity high-pressure solid graphite composite material described in claim 2-9 any one, feature
Be: sintering is 500-800 DEG C of heat preservation 1-12h in step 3).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810891875.3A CN109037643B (en) | 2018-08-07 | 2018-08-07 | High-capacity high-compaction graphite composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810891875.3A CN109037643B (en) | 2018-08-07 | 2018-08-07 | High-capacity high-compaction graphite composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109037643A true CN109037643A (en) | 2018-12-18 |
| CN109037643B CN109037643B (en) | 2020-10-20 |
Family
ID=64649943
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810891875.3A Active CN109037643B (en) | 2018-08-07 | 2018-08-07 | High-capacity high-compaction graphite composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109037643B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111224083A (en) * | 2019-12-03 | 2020-06-02 | 珠海中科兆盈丰新材料科技有限公司 | Graphite/silicate composite material and preparation method thereof |
| CN112467114A (en) * | 2020-11-30 | 2021-03-09 | 湖南中科星城石墨有限公司 | Silica composite material, preparation method thereof and lithium ion battery |
| CN112467116A (en) * | 2020-11-30 | 2021-03-09 | 湖南中科星城石墨有限公司 | Graphite coating material, preparation method thereof and battery cathode |
| CN112645301A (en) * | 2020-12-23 | 2021-04-13 | 福建杉杉科技有限公司 | Particle surface in-situ oxidation and carbon coating modified graphite negative electrode material and preparation method thereof |
| CN114094079A (en) * | 2021-11-17 | 2022-02-25 | 内蒙古恒胜新能源科技有限公司 | Preparation method of quick-charging graphite negative electrode material and lithium ion battery |
| CN114122366A (en) * | 2021-12-07 | 2022-03-01 | 滨州学院 | Cobalt germanate composite microsphere material and preparation method thereof |
| US20220359871A1 (en) * | 2019-06-28 | 2022-11-10 | Panasonic Intellectual Property Management Co., Ltd. | Secondary battery |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150001727A (en) * | 2012-03-28 | 2015-01-06 | 바텔리 메모리얼 인스티튜트 | Energy storage systems having an electrode comprising LixSy |
| CN104617256A (en) * | 2015-01-21 | 2015-05-13 | 上海轻丰新材料科技有限公司 | Nano-zinc oxide-graphite-graphene composite material as well as preparation method and application thereof |
| CN104617301A (en) * | 2015-03-11 | 2015-05-13 | 黑龙江科技大学 | Preparation method of large-size graphene/graphite composite negative pole material |
| CN104934603A (en) * | 2015-05-22 | 2015-09-23 | 田东 | Preparation method of graphene-dopedand carbon-coated modified graphite anode material |
| CN108091833A (en) * | 2017-11-14 | 2018-05-29 | 山东丰元化学股份有限公司 | A kind of high compacted density composite ferric lithium phosphate material and preparation method thereof |
| CN108134088A (en) * | 2016-12-01 | 2018-06-08 | 内蒙古欣源石墨烯科技有限公司 | A kind of rate composite cathode material of lithium ion battery and preparation method thereof |
-
2018
- 2018-08-07 CN CN201810891875.3A patent/CN109037643B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150001727A (en) * | 2012-03-28 | 2015-01-06 | 바텔리 메모리얼 인스티튜트 | Energy storage systems having an electrode comprising LixSy |
| CN104617256A (en) * | 2015-01-21 | 2015-05-13 | 上海轻丰新材料科技有限公司 | Nano-zinc oxide-graphite-graphene composite material as well as preparation method and application thereof |
| CN104617301A (en) * | 2015-03-11 | 2015-05-13 | 黑龙江科技大学 | Preparation method of large-size graphene/graphite composite negative pole material |
| CN104934603A (en) * | 2015-05-22 | 2015-09-23 | 田东 | Preparation method of graphene-dopedand carbon-coated modified graphite anode material |
| CN108134088A (en) * | 2016-12-01 | 2018-06-08 | 内蒙古欣源石墨烯科技有限公司 | A kind of rate composite cathode material of lithium ion battery and preparation method thereof |
| CN108091833A (en) * | 2017-11-14 | 2018-05-29 | 山东丰元化学股份有限公司 | A kind of high compacted density composite ferric lithium phosphate material and preparation method thereof |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20220359871A1 (en) * | 2019-06-28 | 2022-11-10 | Panasonic Intellectual Property Management Co., Ltd. | Secondary battery |
| CN111224083A (en) * | 2019-12-03 | 2020-06-02 | 珠海中科兆盈丰新材料科技有限公司 | Graphite/silicate composite material and preparation method thereof |
| CN111224083B (en) * | 2019-12-03 | 2021-05-14 | 珠海中科兆盈丰新材料科技有限公司 | Graphite/silicate composite material and preparation method thereof |
| CN112467114A (en) * | 2020-11-30 | 2021-03-09 | 湖南中科星城石墨有限公司 | Silica composite material, preparation method thereof and lithium ion battery |
| CN112467116A (en) * | 2020-11-30 | 2021-03-09 | 湖南中科星城石墨有限公司 | Graphite coating material, preparation method thereof and battery cathode |
| CN112645301A (en) * | 2020-12-23 | 2021-04-13 | 福建杉杉科技有限公司 | Particle surface in-situ oxidation and carbon coating modified graphite negative electrode material and preparation method thereof |
| CN112645301B (en) * | 2020-12-23 | 2023-08-15 | 福建杉杉科技有限公司 | Particle surface in-situ oxidation and carbon coated modified graphite negative electrode material and preparation method thereof |
| CN114094079A (en) * | 2021-11-17 | 2022-02-25 | 内蒙古恒胜新能源科技有限公司 | Preparation method of quick-charging graphite negative electrode material and lithium ion battery |
| CN114094079B (en) * | 2021-11-17 | 2024-02-20 | 内蒙古恒胜新能源科技有限公司 | Preparation method of quick-charge graphite anode material and lithium ion battery |
| CN114122366A (en) * | 2021-12-07 | 2022-03-01 | 滨州学院 | Cobalt germanate composite microsphere material and preparation method thereof |
| CN114122366B (en) * | 2021-12-07 | 2023-09-22 | 滨州学院 | Cobalt germanate composite microsphere material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109037643B (en) | 2020-10-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109037643A (en) | A kind of high capacity high-pressure solid graphite composite material and preparation method thereof | |
| CN109004203B (en) | Silicon-carbon composite negative electrode material and preparation method thereof | |
| CN107959010B (en) | Graphite composite material and preparation method thereof | |
| CN114447305B (en) | Multi-carbon-based quick-charge anode composite material and preparation method thereof | |
| CN103346293A (en) | Lithium ion battery cathode material and preparation method thereof as well as lithium ion battery | |
| CN101572327A (en) | Lithium ion battery adopting graphene as cathode material | |
| CN101794874A (en) | Electrode with grapheme as conductive additive and application thereof in lithium ion battery | |
| CN113764644B (en) | Quick-filling composite graphite material and preparation method thereof | |
| CN106992286B (en) | A kind of preparation method of high capacity trielement composite material | |
| CN109659564A (en) | A kind of negative electrode tab and preparation method thereof reducing lithium ion battery impedance | |
| CN113889593A (en) | Preparation method of hard carbon-coated soft carbon composite material | |
| CN114975974A (en) | High-energy-density graphite composite material, preparation method thereof and lithium ion battery | |
| CN108963237B (en) | Preparation method of sodium ion battery negative electrode material | |
| CN111960413B (en) | Modification method of natural graphite negative electrode material | |
| CN105870401A (en) | Application method of graphene as conductive agent to negative electrode slurry of lithium ion battery | |
| CN117352675A (en) | High-magnification graphite composite material, preparation method thereof and battery | |
| CN102255071A (en) | Modified graphite material as well as manufacturing method and application thereof | |
| CN117117121A (en) | Heteroatom doped asphalt-based hard carbon composite material and preparation method thereof | |
| CN116646488A (en) | Pre-lithiated hard carbon composite material, preparation method and application thereof | |
| CN114920242B (en) | Preparation method of high-capacity graphite composite material | |
| CN110504409A (en) | A kind of positive plate and lithium ion battery improving penetrating power | |
| CN113764645B (en) | Preparation method of hard carbon composite material with three-dimensional structure | |
| CN113594461B (en) | Carbon-silicon composite material and preparation method and application thereof | |
| CN108400317A (en) | A kind of integration lithium ion battery silicon/carbon cathode material and preparation method thereof | |
| CN110034300B (en) | Low-temperature-resistant battery electrode and preparation method thereof |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |