CN106941167A - A kind of porous composite negative pole material of lithium ion battery and preparation method thereof - Google Patents
A kind of porous composite negative pole material of lithium ion battery and preparation method thereof Download PDFInfo
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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
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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
- 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
- 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
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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
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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
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- 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 porous composite negative pole material of a kind of lithium ion battery and preparation method thereof, belong to technical field of lithium ion battery electrode.Described preparation method, comprises the following steps：(1) porous graphite material, conductive agent, polymer, pore creating material are well mixed in solvent, obtain Electrospun liquid；(2) Electrospun liquid is subjected to Electrospun and composite fibre is made；(3) under inert gas shielding; composite fibre is first incubated 1h at 300 DEG C; then 0.5h~15h is calcined within the temperature range of 1000~1500 DEG C; room temperature is down to produce or composite fibre first is incubated into 1~2h at 300~320 DEG C; then 0.5~15h is calcined at 1000~1500 DEG C; chemical mordant is added after cooling and removes pore creating material, is cooled down after drying.Porous composite negative pole material prepared by the present invention has good high rate performance, meets the performance requirement of lithium ion quick charge.
Description
Technical field
The present invention relates to porous composite negative pole material of a kind of lithium ion battery and preparation method thereof, belong to lithium ion battery battery
Pole field of material technology.
Background technology
With the industry development of lithium ion battery and widening for application field, for the power density and energy of lithium ion battery
The requirements at the higher level that metric density is proposed, the demand for being suitable for fast charging and discharging and the lithium ion battery in long continuation of the journey life-span is particularly urgent.
The critical material that negative material fills soon as influence lithium ion battery, it is ensured that improve it while negative material high power capacity and quickly fill
Electrical property is the effective way solved the above problems.
Existing graphite cathode material in charging process, lithium ion from the edge of graphite linings be parallel to graphite linings side
Into embedded graphite, and reach that the distance of depths in graphite linings is longer, less diffusion coefficient limits its big multiplying power charging property
Energy.In addition when being prepared into battery and carrying out big multiplying power and charge repeatedly, due to negative material, rapid expanding is shunk repeatedly, is easily caused
Graphite flake layer is peeled off, and the number of contacts between material granule is reduced, and the conductive network in electrode is destroyed, close to ensure energy in addition
The high pressure compression design that degree is carried out causes material void to reduce, and electrolyte permeability is difficult, easily causes electric in high magnification charging process
The increase of pole polarization, the cycle performance for ultimately resulting in battery is deteriorated.
Chinese patent (application publication number：CN 105932320A, data of publication of application：2016.09.07 a kind of stone) is disclosed
The modified method for preparing composite negative pole material of ink, and specifically disclose herein below：Prepared by solution A, prepared by solution B, solution C system
Standby and composite negative pole material prepares four big processes, wherein in solution A preparation process using polymeric matrix, pore creating material, conductive agent,
Use to have arrived in inorganic additive and organic solvent, solution B preparation process makes in pitch and organic solvent, solution C preparation process
Solution A and solution B are used, is finally prepared by composite negative pole material, graphite is added in three-dimensional material mixer and adds solution C
Row stirring, the heating rate of three-dimensional material mixer controls in 2~10 DEG C/min and is heated to 100~160 DEG C, three-dimensional blender during stirring
The rotating speed control of machine is in 100~150 turns/min and stirs 1.0~10h, is hereafter warming up to 600~1000 DEG C and is incubated 6~24h,
Last cool under inert gas shielding produces.Although this application has used boring technique and doping vario-property technology to carry out graphite
It is modified, capacity, specific surface area and the electric conductivity of the composite negative pole material of preparation are improved, but still production and living can not be met
Demand, can not especially meet the demand of quick charge.
The content of the invention
In order to solve the defect of existing lithium ion battery negative material rapid charge characteristic difference, first purpose of the invention
It is that a kind of porous composite negative pole material preparation method available for quick charge is provided；Second object of the present invention is to carry
For a kind of porous composite negative pole material of the directly obtained quick charge of this method.
To achieve these goals, the technical solution adopted by the present invention is as follows：
A kind of preparation method of the porous composite negative pole material of lithium ion battery, comprises the following steps：
(1) porous graphite material, conductive agent, polymer, the first pore creating material are well mixed in solvent, obtain Electrospun
Liquid；
(2) Electrospun liquid is subjected to Electrospun and composite fibre is made；
(3) under inert gas shielding, composite fibre is first incubated 1~2h at 300~320 DEG C, then 1000~
1500 DEG C of calcining 0.5h~15h, pyrolytic removes pore creating material, and cooling is produced；
Or
(a) porous graphite material, conductive agent, polymer, the second pore creating material are well mixed in solvent, obtain Electrospun
Liquid；
(b) Electrospun liquid is subjected to Electrospun and composite fibre is made；
(c) composite fibre is first incubated 1~2h at 300~320 DEG C, then calcines 0.5~15h at 1000~1500 DEG C,
Chemical mordant is added after cooling and removes pore creating material, is cooled down after drying.
Porous graphite material, conductive agent described in step (1), polymer, the mass ratio of the first pore creating material are：(10~
30)：(0.1~7)：(8~30)：(5~15)；Porous graphite material, conductive agent, polymer described in step (a), second are made
The mass ratio of hole agent is：(10~30)：(0.1~7)：(8~30)：(5~15).
Porous graphite material in more preferably described Electrospun liquid, conductive agent, polymer, pore creating material, solvent
Mass ratio is：(10~30)：(0.1~7)：(8~30)：(5~15)：(100).
Described solvent is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide, N- crassitudes
Ketone, ethylene carbonate, the one or more of dimethyl furan, but not limited to this.
In the preparation method of the described porous composite negative pole material of lithium ion battery, porous graphite material used is profit
Graphite is impregnated with the alkaline aqueous solution of alkali metal or alkali metal, by being heat-treated and then shape to the graphite after separation
Into porous material.
In the preparation method of the described porous composite negative pole material of lithium ion battery, described porous graphite material is tool
Have one or more kinds of compound in the Delanium, native graphite, carbonaceous mesophase spherules of loose structure.
In the preparation method of the described porous composite negative pole material of lithium ion battery, described porous graphite material it is flat
Equal particle diameter D50For 3~15 μm.
In the preparation method of the described porous composite negative pole material of lithium ion battery, the system of described porous graphite material
Preparation Method comprises the following steps：By Delanium, native graphite, carbonaceous mesophase spherules or two or more combinations in alkaline water
In solution impregnate 5min~48h, dipping temperature control at 20 DEG C~60 DEG C, then under inert gas shielding 500 DEG C~
1200 DEG C of heat treatment 0.5h~48h, are cleaned with water, are drying to obtain.
Described alkaline aqueous solution is the NaOH aqueous solution, the KOH aqueous solution etc..
The concentration of described alkaline aqueous solution is preferably 0.05M~15M.
In the preparation method of the described porous composite negative pole material of lithium ion battery, the first described pore creating material is organic
Pore creating material；The second described pore creating material is oxide pore creating material.Pore creating material is added in electrospinning liquid, it is multiple by being made after Electrospun
Condensating fiber, then by thermal decomposition, solvent in organic solvent or chemical attack method remove composite fibre in pore-creating
Agent increases the porosity of negative material so as to be internally formed hole in composite fibre, adds the passage that lithium ion passes in and out graphite,
Diffusion length of the lithium ion in graphite layers is shortened, so as to improve efficiency of transmission of the lithium ion in graphite.
Described organic pore-forming agents are polystyrene, polyvinyl alcohol, polyethylene, polyvinyl acetate, polymethylacrylic acid
One kind in methyl esters.
Described oxide pore creating material is one kind in silica, titanium dioxide, zinc oxide, cupric oxide.
Described chemical mordant be mass fraction be 5~20% hydrochloric acid, mass fraction be 5~20% sulfuric acid, matter
Measure fraction be 5~15% hydrofluoric acid, mass fraction be 20~60% sodium hydroxide solution in one kind.
In the preparation method of the described porous composite negative pole material of lithium ion battery, described conductive agent is acetylene black,
One or more in conductive black, CNT, nitrogen-doped carbon nanometer pipe, graphene, nitrogen-doped graphene, carbon fiber
Composite.
In the preparation method of the described porous composite negative pole material of lithium ion battery, described polymer is polypropylene
At least one in nitrile, polyaniline, polypyrrole, polyimides.
In the preparation method of the described porous composite negative pole material of lithium ion battery, the technological parameter of the Electrospun
For：Voltage：5~20KV, the speed of Electrospun is that the distance between the μ L/min of 10 μ L/min~20, motor is 15cm~20cm.
One kind is using the porous composite negative pole material of lithium ion battery made from above-mentioned preparation method.
The porous composite negative pole material that the present invention is provided, one side loose structure adds the logical of lithium ion turnover graphite linings
Road, shortens diffusion length of the lithium ion in graphite layers, while being conducive to the rapid osmotic of electrolyte, improves the suction of material
Fluidity energy, reduces the polarization during quick charge, the volumetric expansion of graphite when alleviating charging, on the other hand, introducing
Conductive agent adds the electric conductivity of graphite so that negative material of the invention has good high rate performance, meets lithium-ion electric
The requirement of the big multiplying power charging performance in pond.
Brief description of the drawings
Fig. 1 is porous composite negative pole material structural representation in embodiment 1, wherein 1 is porous carbon materials, 2 be conductive agent,
3 be carbon fiber soft carbon layer.
Embodiment
Below by embodiment, the present invention is described in further detail.Specific embodiment described herein is only used for
The present invention is explained, is not intended to limit the present invention.
Embodiment 1
Porous composite negative pole material structural representation such as Fig. 1 in the present embodiment, wherein 1 is porous carbon materials, 2 be conduction
Agent, 3 be carbon fiber soft carbon layer.
The preparation method of the porous composite negative pole material of porous lithium ion cell of the present embodiment comprises the following steps：
1) preparation of porous graphite material：Under the conditions of 25 DEG C of room temperature, by average grain diameter D50For 10 μm, specific surface area is
1.2m2/ g Delanium powder soaks 10 hours in the 5M KOH aqueous solution；Then, powdered graphite is divided by vacuum filter
From, in argon gas atmosphere, handled 2 hours at 800 DEG C of temperature, powdered graphite is cleaned with deionized water, it is finally dry at 60 DEG C
Obtain porous artificial stone ink within 36 hours；
2) preparation of Electrospun solution：By 5 parts of polymethyl methacrylates, 10 parts of polyacrylonitrile, 0.1 part of CNT,
10 parts of porous artificial stone ink are dispersed in 100 parts of DMFs, are produced；
3) preparation of porous composite negative pole material：Under the conditions of 25 DEG C of room temperature, by above-mentioned Electrospun solution 15kV electricity
Pressure, carries out Electrospun with 1mL/h speed and composite fibre is made, interelectrode distance is 20cm, and aluminium foil is used as passive electrode；
Composite fibre is warming up to 300 DEG C of holding 1h with 1.5 DEG C/min in stove, 1100 DEG C of holding 3h are then warming up to 2.5 DEG C/h,
Be down to after room temperature produce it is composite porous；Argon gas is passed through as protective atmosphere in whole calcination process.
Embodiment 2
Step 2 in the present embodiment) it is middle using 0.5 part of CNT, other are in the same manner as in Example 1.
Embodiment 3
1) preparation of porous graphite material：Under the conditions of 25 DEG C of room temperature, by average grain diameter D50For 10 μm, specific surface area is
1.2m2/ g Delanium powder soaks 10 hours in the 5M KOH aqueous solution；Then, powdered graphite is divided by vacuum filter
From, in argon gas atmosphere, handled 2 hours at 800 DEG C of temperature, powdered graphite is cleaned with deionized water, it is finally dry at 60 DEG C
Obtain porous artificial stone ink within 36 hours；
2) preparation of Electrospun solution：10 parts of polyacrylonitrile are dissolved in 100 parts of DMFs, claimed successively
Take 0.3 part of CNT, 15 parts of porous artificial stone ink, 5 parts of SiO2Ultrasound is dispersed in the solution, wherein, SiO2Nano-particle
Diameter is in 50nm；
3) preparation of porous composite negative pole material：Under the conditions of 25 DEG C of room temperature, by above-mentioned Electrospun solution 12kV electricity
Pressure, carries out Electrospun with 1mL/h speed and composite fibre is made, interelectrode distance is 18cm, and aluminium foil is used as passive electrode；
Composite fibre is warming up to 300 DEG C of holding 1h with 1.5 DEG C/min in stove, 1100 DEG C of holding 3h are then warming up to 2.5 DEG C/h,
It is down to after room temperature and obtains SiO2/ fiber C.By composite fibre, (concentration is 20%~60%) soaks 10h in concentrated NaOH solution, goes
Ionized water is washed to after neutrality, is drying to obtain porous composite negative pole material.
Embodiment 4
1) preparation of porous graphite material：Under the conditions of 25 DEG C of room temperature, by average grain diameter D50For 12 μm, specific surface area is
2.5m2/ g natural graphite powder is soaked 12 hours in the 2M NaOH aqueous solution；Then, by vacuum filter by powdered graphite
Separation, 1 hour (900 DEG C of temperature) is handled in argon gas atmosphere, powdered graphite is cleaned with deionized water, is finally dried at 50 DEG C
Obtain porous native graphite within 40 hours；
2) preparation of Electrospun solution：By 6 parts of polymethyl methacrylates, 12 parts of polyacrylonitrile, 0.5 part of CNT,
11.5 parts of porous native graphites are dispersed in 100 parts of N, the dimethylformamides of N- bis-, are produced.
3) preparation of porous composite negative pole material：Under the conditions of 25 DEG C of room temperature, by above-mentioned Electrospun solution 13kV electricity
Pressure, carries out Electrospun with 1.3mL/h speed and composite fibre is made, interelectrode distance is 15cm, and aluminium foil is used as collection electricity
Pole；Composite fibre is warming up to 320 DEG C of holding 2h with 2 DEG C/min in stove, 1000 DEG C of holding 4h are then warming up to 3 DEG C/h,
Be down to after room temperature produce it is composite porous；Argon gas is passed through as protective atmosphere in whole calcination process.
Embodiment 5
The step 2 of the present embodiment) the middle graphene replacement CNT using phase homogenous quantities, other are same as Example 1.
Embodiment 6
1) preparation of porous graphite material：Under the conditions of 25 DEG C of room temperature, by average grain diameter D50For 12 μm, specific surface area is
2.5m2/ g natural graphite powder is soaked 12 hours in the 2M NaOH aqueous solution；Then, by vacuum filter by powdered graphite
Separation, 1 hour (900 DEG C of temperature) is handled in argon gas atmosphere, powdered graphite is cleaned with deionized water, is finally dried at 50 DEG C
Obtain porous native graphite within 40 hours；
2) preparation of Electrospun solution：By 15 parts of polymethyl methacrylates, 30 parts of polyacrylonitrile, 7 parts of CNTs, 30
The porous native graphite of part is dispersed in 100 parts of N, the dimethylformamides of N- bis-, is produced.
3) preparation of porous composite negative pole material：Under the conditions of 25 DEG C of room temperature, by above-mentioned Electrospun solution 13kV electricity
Pressure, carries out Electrospun with 1.3mL/h speed and composite fibre is made, interelectrode distance is 15cm, and aluminium foil is used as collection electricity
Pole；Composite fibre is warming up to 320 DEG C of holding 2h with 2 DEG C/min in stove, 1000 DEG C of holding 4h are then warming up to 3 DEG C/h,
Be down to after room temperature produce it is composite porous；Argon gas is passed through as protective atmosphere in whole calcination process.
Embodiment 7
1) preparation of porous graphite material：Under the conditions of 25 DEG C of room temperature, by average grain diameter D50For 12 μm, specific surface area is
2.5m2/ g natural graphite powder is soaked 12 hours in the 2M NaOH aqueous solution；Then, by vacuum filter by powdered graphite
Separation, 1 hour (900 DEG C of temperature) is handled in argon gas atmosphere, powdered graphite is cleaned with deionized water, is finally dried at 50 DEG C
Obtain porous native graphite within 40 hours；
2) preparation of Electrospun solution：By 5 parts of polymethyl methacrylates, 8 parts of polyacrylonitrile, 0.5 part of CNT, 10
The porous native graphite of part is dispersed in 100 parts of N, the dimethylformamides of N- bis-, is produced.
3) preparation of porous composite negative pole material：Under the conditions of 25 DEG C of room temperature, by above-mentioned Electrospun solution 13kV electricity
Pressure, carries out Electrospun with 1.3mL/h speed and composite fibre is made, interelectrode distance is 15cm, and aluminium foil is used as collection electricity
Pole；Composite fibre is warming up to 320 DEG C of holding 2h with 2 DEG C/min in stove, 1000 DEG C of holding 4h are then warming up to 3 DEG C/h,
Be down to after room temperature produce it is composite porous；Argon gas is passed through as protective atmosphere in whole calcination process.
Comparative example 1
Composite negative pole material, people are prepared as raw material using graphous graphite powder in the same manner as in Example 1 in this comparative example
Make the average grain diameter D of graphite powder50For 10 μm, specific surface area is 1.2m2/g；Graphous graphite powder is not carried out strictly according to the facts in preparation process
Apply the step 1 of example 1) in processing, the preparation method for preparing Electrospun solution and composite negative pole material is same as Example 1.
Comparative example 2
With with the step 1 of embodiment 1) in identical mode prepare porous graphite material, the porous graphite material is negative pole
Material.
Test example
Electric discharge appearance is carried out to the negative material in embodiment 1~3 and comparative example 1,2 using button cell method of testing
The test of amount, first efficiency and rapid charging performance, is as a result listed in table 1.
Button cell method of testing of the invention used is：Conductive black is added in the LA132 aqueous solution, graphite is then added
Sample, after stirring, is evenly coated in copper foil surface and pole piece is made.The pole piece coated is put into 100 DEG C of vacuum drying chambers very
Sky dries 6h, takes out pole piece roll-in on roll squeezer standby.Button cell is assemblied in the glove box full of Ar gas and carried out, electrolysis
Liquid is 1.2MLiPF6, EC:DEC:DMC=1:1:1 (volume ratio), metal lithium sheet is to electrode.Volume test is in blue electric tester
It is upper to carry out.
Button cell tests work step：0.005V is charged to 0.1C first, shelves 5 minutes, 2.5V is discharged to 0.1C, followed
Ring is twice；0.005V is charged to 6C, shelved 5 minutes.
Under the conditions of 25 DEG C ± 2 DEG C, parallel testing button cell 8, remove exceptional value after average (according to
When GB4883-1985 regulation measured values exceed twice of standard deviation of average value, the numerical value is exceptional value).Calculated using below equation
Negative material gram volume：
C=Cave/ [(M electrode-M Copper Foils) × active material percentage]
Wherein C：Negative material gram volume mAh/g；Cave：Button cell average discharge capacity mAh；M electrodes：Negative plate weight
Measure g；M Copper Foils：The weight g of Copper Foil.
The button cell of table 1 is tested
The present invention first impregnates graphitic carbon material in alkaline aqueous solution, is then heat-treated so that the carbon of carbon material
Certain peel off is formed between layer to aoxidize, certain fault of construction is caused so that the specific surface area increase of carbon material, is conducive to conduction
Agent, polymer, pore creating material are fully contacted with it, are evenly distributed between component.Composite fibre is made by Electrospun, it is obtained multiple
Be evenly distributed between condensating fiber each component, during being conducive to follow-up pore-creating, form that pore size distribution is uniform, uniform pore diameter it is compound
Negative material.Finally by calcining or calcining plus chemical mordant processing, remove pore creating material and composite negative pole material is made.Forging
During burning, high treatment temperature can remove the defect on carbon material, for example, remove some oxygen-containing functional groups and carbon-coating side
Edge malformed structure, so that the electric conductivity of material gets a promotion.
Composite negative pole material produced by the present invention, even aperture distribution, with higher specific surface area, is the biography of lithium ion
It is defeated that good transmission channel, the transmission of favourable lithium ion are provided, and the composite negative pole material defect of the present invention is less, electric conductivity
Height, structural stability is good.Tested by above-mentioned button cell, it can be found that its good structure and high specific surface area can
Receive and transmit more lithium ions, cause its initial capacity apparently higher than the initial capacity in comparative example, pass through rate of charge
Characteristic test, illustrates the composite negative pole material Stability Analysis of Structures in the present invention, and defect is less, and capability retention is high.It is of the present invention
Porous carbon compound cathode materials prepared by method have excellent chemical property, especially possess outstanding high rate performance.
Claims (10)
1. a kind of preparation method of the porous composite negative pole material of lithium ion battery, it is characterised in that comprise the following steps：
(1) porous graphite material, conductive agent, polymer, the first pore creating material are well mixed in solvent, obtain Electrospun liquid；
(2) Electrospun liquid is subjected to Electrospun and composite fibre is made；
(3) under inert gas shielding, composite fibre is first incubated 1~2h at 300~320 DEG C, then at 1000~1500 DEG C
0.5h~15h is calcined, pyrolytic removes pore creating material, and cooling is produced；
Or
(a) porous graphite material, conductive agent, polymer, the second pore creating material are well mixed in solvent, obtain Electrospun liquid；
(b) Electrospun liquid is subjected to Electrospun and composite fibre is made；
(c) composite fibre is first incubated 1~2h at 300~320 DEG C, 0.5~15h, cooling is then calcined at 1000~1500 DEG C
Chemical mordant is added afterwards and removes pore creating material, is cooled down after drying.
2. the preparation method of the porous composite negative pole material of lithium ion battery according to claim 1, it is characterised in that step
(1) porous graphite material, conductive agent described in, polymer, the mass ratio of the first pore creating material are：(10~30)：(0.1~7)：
(8~30)：(5~15)；Porous graphite material, conductive agent described in step (a), polymer, the mass ratio of the second pore creating material
For：(10~30)：(0.1~7)：(8~30)：(5~15).
3. the preparation method of the porous composite negative pole material of lithium ion battery according to claim 1, it is characterised in that described
Porous graphite material be the Delanium with loose structure, native graphite, carbonaceous mesophase spherules in one or two kinds of with
On composite.
4. the preparation method of the porous composite negative pole material of lithium ion battery according to claim 3, it is characterised in that described
Porous graphite material average grain diameter D50For 3~15 μm, its specific surface area is 1.0~2.5m2/g。
5. the preparation method of the porous composite negative pole material of lithium ion battery according to claim 3, it is characterised in that described
The preparation method of porous graphite material comprise the following steps：By a kind of in Delanium, native graphite, carbonaceous mesophase spherules or
The two or more composite of person impregnates 5min~48h in alkaline aqueous solution, and dipping temperature is 20 DEG C~60 DEG C, then lazy
Property gas shield under 500 DEG C~1200 DEG C be heat-treated 0.5h~48h, cleaned, be drying to obtain with water.
6. the preparation method of the porous composite negative pole material of lithium ion battery according to claim 1, it is characterised in that described
The first pore creating material be organic pore-forming agents；The second described pore creating material is oxide pore creating material；Wherein described organic pore-forming agents
For one kind in polystyrene, polyvinyl alcohol, polyethylene, polyvinyl acetate, polymethyl methacrylate；Described oxide
Pore creating material is one kind in silica, titanium dioxide, zinc oxide, cupric oxide.
7. the preparation method of the porous composite negative pole material of lithium ion battery according to claim 1, it is characterised in that described
Conductive agent be acetylene black, conductive black, CNT, nitrogen-doped carbon nanometer pipe, graphene, nitrogen-doped graphene, carbon fiber
In one or more.
8. the preparation method of the porous composite negative pole material of lithium ion battery according to claim 1, it is characterised in that described
Polymer be polyacrylonitrile, polyaniline, polypyrrole, polyimides in one or more.
9. the preparation method of the porous composite negative pole material of lithium ion battery according to claim 1, it is characterised in that described
The technological parameter of Electrospun is：Voltage is 5~20kV, and the speed of Electrospun is the μ of 10 μ L/min~20 L/min, it is interelectrode away from
From for 15cm~20cm.
10. porous composite negative pole material made from the preparation method described in a kind of use claim 1.
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN108172890A (en) * | 2017-12-22 | 2018-06-15 | 成都市银隆新能源有限公司 | A kind of preparation method of battery and its pole piece |
| CN108682830A (en) * | 2018-06-11 | 2018-10-19 | 清华大学深圳研究生院 | A kind of silicon-carbon composite cathode material of lithium ion battery and preparation method thereof |
| CN109546110A (en) * | 2018-11-13 | 2019-03-29 | 大同新成新材料股份有限公司 | A kind of composite graphite electrode preparation method and preparation facilities |
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| CN109763263A (en) * | 2019-01-31 | 2019-05-17 | 兰溪致德新能源材料有限公司 | The technique that electrostatic spinning prepares silicon-carbon ear pole material |
| CN109809385A (en) * | 2019-01-25 | 2019-05-28 | 安徽益佳通电池有限公司 | A kind of lithium ion battery negative material of height ratio capacity and preparation method thereof |
| CN110034292A (en) * | 2019-04-30 | 2019-07-19 | 河北工业大学 | A kind of 3-D ordered multiporous polypyrrole/zinc oxide lithium ion battery negative material and preparation method |
| CN110176634A (en) * | 2019-05-16 | 2019-08-27 | 湖北锂诺新能源科技有限公司 | A kind of preparation process of low bulk lithium ion battery |
| CN110311125A (en) * | 2019-08-15 | 2019-10-08 | 马鞍山科达普锐能源科技有限公司 | A kind of lithium-ion battery silicon-carbon anode material and preparation method thereof |
| CN111411450A (en) * | 2020-02-17 | 2020-07-14 | 五邑大学 | Preparation method and application of flexible nano-cobweb-structured conductive polyurethane film |
| CN111864203A (en) * | 2019-04-28 | 2020-10-30 | 中国科学院上海硅酸盐研究所 | High-capacitance lithium-carbon negative electrode material and preparation method and application thereof |
| CN113104845A (en) * | 2020-01-13 | 2021-07-13 | 上海昱瓴新能源科技有限公司 | Method for preparing porous artificial graphite cathode material by using electrode joint powder as raw material |
| CN114530597A (en) * | 2022-01-26 | 2022-05-24 | 内蒙古斯诺新材料科技有限公司 | Modified natural graphite and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107623120A (en) * | 2017-10-12 | 2018-01-23 | 中国科学技术大学 | Flexible electrode material, its preparation method and lithium/sodium-ion battery |
| CN108172890A (en) * | 2017-12-22 | 2018-06-15 | 成都市银隆新能源有限公司 | A kind of preparation method of battery and its pole piece |
| CN108682830B (en) * | 2018-06-11 | 2020-08-18 | 清华大学深圳研究生院 | Silicon-carbon composite negative electrode material of lithium ion battery and preparation method thereof |
| CN108682830A (en) * | 2018-06-11 | 2018-10-19 | 清华大学深圳研究生院 | A kind of silicon-carbon composite cathode material of lithium ion battery and preparation method thereof |
| CN109546110A (en) * | 2018-11-13 | 2019-03-29 | 大同新成新材料股份有限公司 | A kind of composite graphite electrode preparation method and preparation facilities |
| CN109734084A (en) * | 2018-12-29 | 2019-05-10 | 东莞市鸿亿导热材料有限公司 | A kind of foam stone ink sheet and preparation method thereof for cathode of lithium battery |
| CN109809385A (en) * | 2019-01-25 | 2019-05-28 | 安徽益佳通电池有限公司 | A kind of lithium ion battery negative material of height ratio capacity and preparation method thereof |
| CN109763263A (en) * | 2019-01-31 | 2019-05-17 | 兰溪致德新能源材料有限公司 | The technique that electrostatic spinning prepares silicon-carbon ear pole material |
| CN111864203A (en) * | 2019-04-28 | 2020-10-30 | 中国科学院上海硅酸盐研究所 | High-capacitance lithium-carbon negative electrode material and preparation method and application thereof |
| CN111864203B (en) * | 2019-04-28 | 2022-01-04 | 中国科学院上海硅酸盐研究所 | High-capacitance lithium-carbon negative electrode material and preparation method and application thereof |
| CN110034292A (en) * | 2019-04-30 | 2019-07-19 | 河北工业大学 | A kind of 3-D ordered multiporous polypyrrole/zinc oxide lithium ion battery negative material and preparation method |
| CN110034292B (en) * | 2019-04-30 | 2022-05-24 | 河北工业大学 | Three-dimensional ordered porous polypyrrole/zinc oxide lithium ion battery negative electrode material and preparation method thereof |
| CN110176634A (en) * | 2019-05-16 | 2019-08-27 | 湖北锂诺新能源科技有限公司 | A kind of preparation process of low bulk lithium ion battery |
| CN110311125A (en) * | 2019-08-15 | 2019-10-08 | 马鞍山科达普锐能源科技有限公司 | A kind of lithium-ion battery silicon-carbon anode material and preparation method thereof |
| CN113104845A (en) * | 2020-01-13 | 2021-07-13 | 上海昱瓴新能源科技有限公司 | Method for preparing porous artificial graphite cathode material by using electrode joint powder as raw material |
| CN111411450A (en) * | 2020-02-17 | 2020-07-14 | 五邑大学 | Preparation method and application of flexible nano-cobweb-structured conductive polyurethane film |
| CN114530597A (en) * | 2022-01-26 | 2022-05-24 | 内蒙古斯诺新材料科技有限公司 | Modified natural graphite and preparation method thereof |
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