CN105161725B - A kind of preparation method of cathode material for lithium-ion power battery - Google Patents
A kind of preparation method of cathode material for lithium-ion power battery 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on 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
- 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
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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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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a kind of preparation method of cathode material for lithium-ion power battery, belong to technical field of lithium ion.This method comprises the following steps：1) graphite material or carbonaceous mesophase spherules or asphalt pyrolysis carbon are added in dopant solution, temperature is 10 80 DEG C, impregnates 5 60h, is filtered, and drying, obtains doping presoma；The dopant is water soluble lithium compounds or water soluble lithium compounds and transition metal salt；2) the obtained doping presoma of step 1) is mixed with cladding carbon source, under protective atmosphere, 800 2800 DEG C of 2 20h of insulation, cooling, produced；The cladding carbon source and the mass ratio of the doping presoma are 0.5 20:100.The preparation method of the cathode material for lithium-ion power battery of the present invention, improves the electric conductivity of negative material, and reduces irreversible lithium loss, improves the specific capacity and cycle performance of negative material.
Description
Technical field
The present invention relates to a kind of preparation method of cathode material for lithium-ion power battery, belongs to lithium ion battery technology neck
Domain.
Background technology
Become increasingly conspicuous with development of world economy, the problems such as energy shortage, environmental pollution, renewable, free of contamination new energy
Source technology increasingly attracts attention, and high-efficiency energy-storage device is exactly one of which.In high-efficiency energy-storage device, lithium ion battery is with it
The advantage such as high-energy-density, high voltage, long circulation life, pollution-free, memory-less effect turns into following and most developed for 10~20 years
One of high-efficiency energy-storage device of potentiality.
With the continuous expansion of lithium ion battery applications scope, performance requirement of the different application field to lithium ion battery
More and more higher.In the factors for influenceing performance of lithium ion battery, electrode material plays decision to the performance of lithium ion battery
The effect of property.Research in terms of currently used positive electrode makes the performance of conventional positive electrode constantly be lifted and moved closer to
Its limit, already close to its theoretical capacity, the space continued to lift up is constantly reduced the specific capacity of a variety of positive electrodes.In view of
This, the raising to negative material performance just seems more meaningful.In numerous negative materials, graphitized carbon material due to
Good layer structure, it is very suitable for the insertion and deintercalation of lithium ion, compound L i-GIC has between graphite-lithium layer of formation
There is very high specific capacity, close to LiC6Theoretical specific capacity 372mAh/g；Simultaneously also have good charging/discharging voltage platform and
Relatively low embedding de- lithium current potential, with conventional positive electrode, such as LiCoO2、LiMn2O4Preferable etc. matching, the battery formed is put down
Equal voltage is high, and electric discharge is steady, therefore current commercial lithium-ion batteries are largely using graphite-like carbon material as negative material.
But the shortcomings that graphite material, is also clearly, first, graphite material has height because degree of graphitization is high
The graphite laminate structure of orientation, poor with the compatibility of organic solvent, in first charge-discharge, with organic solvent stone can occur for lithium
Common insertion between layer of ink, cause graphite linings peel off, graphite particle is burst apart and efflorescence, cause electrode structure to destroy, battery
Cycle performance reduces.Second, because the laminated structure of graphite only allows border of the lithium ion along graphite crystal embedded and deviates from, instead
Answer area small, diffusion path length, be generally not suitable for high current charge-discharge, limit lithium ion battery in fields such as electrokinetic cells
Development.3rd, the sheet-like particle with big draw ratio is easily formed in crushing process of the graphite cathode material when prepared by powder,
Sheet-like particle is easily formed in parallel with aligning for collector in the nipping process when prepared by electrode, in repeated charge process
In, lithium ion enters and abjection graphite crystal inside can cause the c-axis direction of graphite to produce large strain, causes electrode structure to break
It is bad, it have impact on cycle performance；The result that exfoliated graphite particles align can also cause lithium ion to enter from the side of graphite crystal
The resistance for entering and deviating from increases, and its fast charging and discharging performance is deteriorated.4th, due to sheet-like particle graphite crystal with it is spherical and
Blocky graphite particle easily causes lithium ion that irreversible insertion occurs, causes lithium-ion electric compared to having larger specific surface area
Pond negative material has larger irreversible capacity during first charge-discharge.
In order to improve the combination property of graphite material, relatively common method is modified to graphite material, such as doping and
Cladding.Publication No. CN1697215A Chinese invention patent (publication date is on November 16th, 2005) discloses a kind of lithium ion
The preparation method of cell composite carbon negative polar material, specifically disclose its preparation method and handled, at purifying including crushing, spheroidization
The step such as reason, washing, multivalent state transition metal salt solution dipping, Coated with Organic Matter, carbonization.Negative material made from this method has
There are preferable removal lithium embedded ability and cyclical stability.But above-mentioned negative material specific capacity is relatively low, cycle performance still needs to be carried
It is high.
The content of the invention
It is an object of the invention to provide a kind of specific capacity height, the cathode material for lithium-ion power battery of good cycle
Preparation method.
In order to realize the above object the technical scheme of the preparation method of the cathode material for lithium-ion power battery of the present invention
It is as follows：
A kind of preparation method of cathode material for lithium-ion power battery, comprises the following steps：
1) graphite material or carbonaceous mesophase spherules or asphalt pyrolysis carbon are added in the dopant aqueous solution, temperature 10-80
DEG C, 5-60h is impregnated, is filtered, drying, obtains doping presoma；
The graphite material is one kind in native graphite, Delanium；
The dopant is water soluble lithium compounds or water soluble lithium compounds and water-soluble transition metal salt；
When dopant is water soluble lithium compounds, the mass percent concentration of the dopant aqueous solution is 0.1-10%, water-soluble
Property lithium compound and graphite material or the mass ratio of carbonaceous mesophase spherules or asphalt pyrolysis carbon be 0.1-10:100；
When dopant is water soluble lithium compounds and water-soluble transition metal salt, water-soluble lithiumation is closed in the dopant aqueous solution
The mass percent concentration of thing is 0.1-10%, and the concentration of water-soluble transition metal salt is 0.2-8%, water soluble lithium compounds,
Water-soluble transition metal salt and the mass ratio of graphite material or carbonaceous mesophase spherules or asphalt pyrolysis carbon are 0.1-10:0.2-8：
100；
2) the obtained doping presoma of step 1) is mixed with cladding carbon source, under protective atmosphere, 800-2800 DEG C of insulation
2-20h, composite is obtained, cool down, produce cathode material for lithium-ion power battery；
The cladding carbon source and the mass ratio of the doping presoma are 0.5-20:100.
The preparation method of the cathode material for lithium-ion power battery of the present invention by graphite material or carbonaceous mesophase spherules or
Asphalt pyrolysis carbon impregnates in the dopant solution of water soluble lithium compounds or water soluble lithium compounds and transition metal salt, when mixing
Miscellaneous dose when being water soluble lithium compounds, dipping can in graphite material or carbonaceous mesophase spherules or asphalt pyrolysis carbon elements doped lithium, energy
A certain amount of extra lithium enough is provided for negative material, graphite material or carbonaceous mesophase spherules or pitch heat during supplemented with discharge and recharge
The irreversible lithium loss of carbon is solved, improves the capacity of negative material on the whole.When dopant includes water-soluble lithium chemical combination simultaneously
When thing and transition metal salt, due to transition metal participate in electrode reaction after, can fix a part lithium, cause it is certain not
Reversible lithium loses, and lithium compound can provide extra lithium, be lost supplemented with lithium caused by transition metal, with transition metal
Element acts synergistically, the common specific capacity and structural stability for improving negative material.
Composite after being cooled down in the step 2) passes through nano-carbon material modification, and the nano-carbon material is modified
The step of processing, includes：
Nano-carbon material is mixed with the composite after being cooled down in the step 2), it is described to be mixed into solid phase mixing or liquid
Mix, add water, be uniformly dispersed using ultrasonic vibration, then in 100-250 DEG C of spray drying, composite table after the cooling period
Face forms one layer of layer of nanomaterial；
The nano-carbon material is 0.1-3.0 with the mass ratio with the composite after cooling in the step 2):100.
Above-mentioned nano-carbon material can reduce graphite material or carbonaceous mesophase spherules or asphalt pyrolysis carbon in charge and discharge process
Volume Changes amplitude, be advantageous to keep negative material Stability Analysis of Structures, improve its cycle performance.In addition, nano-carbon material material
Material has stronger electric conductivity, is advantageous to improve the multiplying power discharging property of negative material.
The nano-carbon material is one kind in CNT, carbon nano-fiber, graphene.These nano-carbon materials are in stone
Ink material or carbonaceous mesophase spherules or asphalt pyrolysis carbon surface form the network structure intersected, and itself has stronger toughness, entered
One step enhances the structural stability of material.
The thickness of layer of nanomaterial is excessive easily to cause impedance when Lithium-ion embeding and abjection to increase, and is unfavorable for big multiplying power
Discharge and recharge, the thickness of layer of nanomaterial it is too small then again can weaker its graphite material or carbonaceous mesophase spherules or asphalt pyrolysis carbon are become
The inhibitory action of shape, in general, the thickness of the layer of nanomaterial is 1-400nm.
In order to improve the regular degree of the particle of graphite material or carbonaceous mesophase spherules or asphalt pyrolysis carbon, and it is easy to adulterate
And cladding, the graphite material or carbonaceous mesophase spherules or asphalt pyrolysis carbon are by crushing, spheroidization processing.
In order to avoid influence of the impurity to cladding processing, graphite material or carbonaceous mesophase spherules or asphalt pyrolysis the carbon warp
Cross purification process.
The purification process is to take graphite material or carbonaceous mesophase spherules or asphalt pyrolysis carbon, is added to jointly with oxidant
In reactor, add water to be stirred 5-15min, 1-20h is stirred at reflux at a temperature of 50-360 DEG C, add complexing agent progress
Complex reaction, complex reaction time are 2-10h.Add 10~60min of water washing after complex reaction, then carry out centrifugal dehydration, then
Moisture is dried at 100~360 DEG C less than 0.2%.Micro- Fe, Cu in the material that purification process obtains, Cr, Na,
Each individual event content of Ca, Zn, Mn, Al, Si is respectively less than 50ppm, and the summation of above-mentioned micronutrient levels is less than 150ppm.
The oxidant that above-mentioned purification process uses is hydrogen peroxide, Peracetic acid, chlorine dioxide, chlorine, sodium hydroxide, dense sulphur
Any two or three of mixture in acid, nitric acid, concentrated hydrochloric acid, perchloric acid.
The complexing agent that above-mentioned purification process uses is nitrilotriacetic acid, ferric trichloride, hydrofluoric acid, phosphoric acid, hydrochloric acid or cholic acid network
One kind in mixture.
Neutrality is washed with water to after purification process, is dried.
Water soluble lithium compounds are preferably one kind in lithium nitrate, lithium chloride, lithium hydroxide, lithium acetate.
Transition metal is the one of Ag, Cu, Cr, Fe, Co, Ni, V, Mo, Sn in described water-soluble transition metal salt
Kind.
The cladding carbon source be water soluble polymer or oil-soluble macromolecule, the water soluble polymer be polyvinyl alcohol,
One kind in butadiene-styrene rubber breast SBR, carboxyl methyl cellulose, the oil-soluble macromolecule are polystyrene, polymethylacrylic acid
One kind in methyl esters, polytetrafluoroethylene (PTFE), Kynoar, polyacrylonitrile.
The method mixed in the step 2) is liquid phase coating or melting cladding or solid phase cladding.
Negative material made from the preparation method of the cathode material for lithium-ion power battery of the present invention, by core carbon materials
Lithium compound and transition metal are added in material, improves the electric conductivity of negative material, and reduces irreversible lithium loss, is carried
The high specific capacity and cycle performance of negative material.Its reversible specific capacity is more than 368mAh/g, circulates coulombic efficiency first and is more than
94%, circulate 2000 capability retentions and be more than 80%.With excellent lithium storage performance, and preparation cost is cheap, is adapted to
As each type electric tool, lithium ion battery for electric vehicle negative material.
Embodiment
Technical scheme is further detailed with reference to specific embodiment.
Embodiment 1
The preparation method of the cathode material for lithium-ion power battery of the present embodiment comprises the following steps：
1) pre-process
A. crush：Native graphite is added in high speed disintegrator, 30min is crushed under 2000rpm rotating speed and obtains graphite powder；
The particle diameter of the native graphite is 75 μm；
B. spheroidization is handled：Obtained graphite powder is added in low velocity impact formula nodularization pulverizer, under 500rpm rotating speeds
Shaping and spheroidization processing 240min are carried out, obtains spherical graphite；
C. purification process：The spherical graphite obtained in 100kg steps B is put into reactor, adds sulfuric acid and nitric acid
Mixed acid 35kg, add suitable quantity of water, stir 10min, be stirred at reflux 18h at a temperature of 300 DEG C, add ferric trichloride
15kg, add water to stir into pasty state, react 2h；Add water washing 10min, then carry out centrifugal dehydration, then moisture is dried at 100 DEG C
Content is less than 0.2%, obtains dry graphite powder；
2) presoma is adulterated to prepare
The drying graphite powder obtained in step 1) is added in dopant solution, 5h is impregnated at 25 DEG C, is filtered, is dehydrated, is dried
It is dry, obtain doping presoma；
The dopant is lithium nitrate and silver nitrate, and dopant solution is the aqueous solution of lithium nitrate and silver nitrate, wherein nitre
The concentration of sour lithium is 5%, and the concentration of silver nitrate is 1.7%；
Dopant and the mass ratio of graphite powder dried are：Lithium nitrate：Silver nitrate：Dry graphite powder=5:1.7:100；
3) coat
The doping presoma obtained in step 2) is added in butadiene-styrene rubber (SBR) and mixed, adds water to be uniformly dispersed, 150
It is spray-dried at DEG C, under nitrogen protection, is warming up to 1000 DEG C with 0.5 DEG C/min programming rate, is incubated 2h, obtains compound
Material, room temperature is cooled to, crushed, screening, produced；
The mass ratio for adulterating presoma and butadiene-styrene rubber (SBR) is 100:1.5.
Embodiment 2
The preparation method of the cathode material for lithium-ion power battery of the present embodiment comprises the following steps：
1) pre-process
A. crush：Delanium is added in high speed disintegrator, 120min is crushed under 5000rpm rotating speed and obtains graphite
Powder；The particle diameter of the native graphite is 1000 μm；
B. spheroidization is handled：Obtained graphite powder is added in low velocity impact formula nodularization pulverizer, under 2000rpm rotating speeds
Shaping and spheroidization processing 60min are carried out, obtains spherical graphite；
C. purification process：The spherical graphite obtained in 100kg steps B is put into reactor, adds hydrogen peroxide and mistake
The mixture 35kg of fluoroacetic acid, add suitable quantity of water, stir 5min, be stirred at reflux 12h at a temperature of 100 DEG C, add tri-chlorination
Iron 15kg, add water to stir into pasty state, react 10h；Add water washing 60min, then carry out centrifugal dehydration, then be dried at 360 DEG C
Moisture is less than 0.2%, obtains dry graphite powder；
2) presoma is adulterated to prepare
The drying graphite powder obtained in step 1) is added in dopant solution, 10h is impregnated at 80 DEG C, is filtered, is dehydrated, is dried
It is dry, obtain doping presoma；
The dopant is lithium hydroxide and copper nitrate, and dopant solution is the aqueous solution of lithium hydroxide and copper nitrate, its
The concentration of middle lithium hydroxide is 0.1%, and the concentration of silver nitrate is 0.2%；
Dopant and the mass ratio of graphite powder dried are：Lithium hydroxide：Copper nitrate：Dry graphite powder=0.1:0.2:
100；
3) coat
The doping presoma obtained in step 2) is added in the polyvinyl alcohol of melting and is well mixed, under nitrogen protection,
2800 DEG C are warming up to 20 DEG C/min programming rate, 2h is incubated, obtains composite, be cooled to room temperature, is crushed, screening, is produced；
The mass ratio for adulterating presoma and polyvinyl alcohol is 100:0.5.
Embodiment 3
The preparation method of the cathode material for lithium-ion power battery of the present embodiment comprises the following steps：
1) presoma is adulterated to prepare
Dry carbonaceous mesophase spherules powder is added in dopant solution, 60h is impregnated at 20 DEG C, is filtered, is dehydrated, drying,
Presoma must be adulterated；
The dopant is lithium chloride and nickel nitrate Ni (NO3)2, dopant solution is the aqueous solution of lithium chloride and nickel nitrate,
Wherein the concentration of lithium chloride is 4.5%, and the concentration of nickel nitrate is 5.0%；
Dopant and the mass ratio of carbonaceous mesophase spherules powder dried are：Lithium chloride：Nickel nitrate：Dry carbonaceous mesophase spherules
Powder=4.5:5:100；
2) coat
The doping presoma obtained in step 2) is well mixed with carboxyl methyl cellulose, under nitrogen protection, with 1
DEG C/min programming rate is warming up to 800 DEG C, 20h is incubated, composite is obtained, is cooled to room temperature, is crushed, screening, is produced；
The mass ratio for adulterating presoma and carboxymethyl cellulose is 100:20.
Embodiment 4
The preparation method of the cathode material for lithium-ion power battery of the present embodiment comprises the following steps：
1) pre-process
A. crush：Asphalt pyrolysis carbon is added in high speed disintegrator, 60min is crushed under 4000rpm rotating speed and obtains pitch
It is pyrolyzed carbon dust；The particle diameter of the asphalt pyrolysis carbon is 200 μm；
B. spheroidization is handled：Obtained asphalt pyrolysis carbon dust is added in low velocity impact formula nodularization pulverizer, 1200rpm
Shaping and spheroidization processing 180min are carried out under rotating speed, obtains spheroidization asphalt pyrolysis carbon dust；
C. purification process：The spheroidization asphalt pyrolysis carbon dust obtained in 100kg steps B is put into reactor, adds sulphur
The mixture 35kg of acid and nitric acid, add suitable quantity of water, stir 15min, be stirred at reflux 2h at a temperature of 200 DEG C, add ammonia three
Acetic acid 15kg, add water to stir into pasty state, react 4h；Add water washing 30min, then carry out centrifugal dehydration, then be dried at 200 DEG C
Moisture is less than 0.2%, obtains dry asphalt pyrolysis carbon dust；
2) presoma is adulterated to prepare
The asphalt pyrolysis carbon dust of the drying obtained in step 1) is added in dopant solution, 50h, mistake are impregnated at 30 DEG C
Filter, it is dehydrated, drying, obtains doping presoma；
The dopant is lithium acetate and chromic nitrate Cr (NO3)3, dopant solution is the aqueous solution of lithium acetate and chromic nitrate,
Wherein the concentration of lithium acetate is 10%, and the concentration of chromic nitrate is 8.0%；
Dopant and the mass ratio of asphalt pyrolysis carbon dust dried are：Lithium acetate：Chromic nitrate：Dry asphalt pyrolysis carbon dust
=10:8:100；
3) coat
The doping presoma obtained in step 2) is added in the toluene solution of polystyrene and mixed, solvent evaporated, adds water
It is uniformly dispersed, is spray-dried at 150 DEG C, under nitrogen protection, is warming up to 1200 DEG C with 5 DEG C/min programming rate, protects
Warm 10h, obtains composite, is cooled to room temperature, crushes, and screening, produces；
The mass ratio for adulterating presoma and polystyrene is 100:12.
Embodiment 5
The preparation method of the cathode material for lithium-ion power battery of the present embodiment comprises the following steps：
1) pre-process
A. crush：Native graphite is added in high speed disintegrator, 30min is crushed under 2000rpm rotating speed and obtains graphite powder；
The particle diameter of the asphalt pyrolysis carbon is 75 μm；
B. spheroidization is handled：Obtained graphite powder is added in low velocity impact formula nodularization pulverizer, under 500rpm rotating speeds
Shaping and spheroidization processing 240min are carried out, obtains spherical graphite；
C. purification process：The spherical graphite obtained in 100kg steps B is put into reactor, adds sulfuric acid and nitric acid
Mixture 35kg, add suitable quantity of water, stir 10min, be stirred at reflux 18h at a temperature of 80 DEG C, add nitrilotriacetic acid 15kg,
Add water to stir into pasty state, react 2h；Add water washing 30min, then carry out centrifugal dehydration, then moisture is dried at 200 DEG C
Less than 0.2%, dry graphite powder is obtained；
2) presoma is adulterated to prepare
The drying graphite powder obtained in step 1) is added in dopant solution, 5h is impregnated at 25 DEG C, is filtered, is dehydrated, is dried
It is dry, obtain doping presoma；
The dopant is lithium nitrate, and dopant solution is the aqueous solution of lithium nitrate, and wherein the concentration of lithium nitrate is 5%；
Dopant and the mass ratio of graphite powder dried are：Lithium nitrate：Dry graphite powder=5:100；
3) coat
The doping presoma obtained in step 2) is added in butadiene-styrene rubber and mixed, adds water to be uniformly dispersed, in 150 DEG C of progress
Spray drying, under nitrogen protection, 1000 DEG C are warming up to 0.5 DEG C/min programming rate, 12h is incubated, obtains composite, it is cold
But to room temperature, crush, screening, produce；
The mass ratio for adulterating presoma and butadiene-styrene rubber is 100:1.5.
Embodiment 6
The cathode material for lithium-ion power battery of the present embodiment is the composite wood after the middle cooling of step 3) in embodiment 1
Expect made from one layer of layer of nanomaterial of outer cladding, to concretely comprise the following steps：
CNT is mixed with the composite after being cooled down in the step 3) of embodiment 1, adds water, is disperseed using ultrasonic vibration
Uniformly, 150 DEG C of spray drying, one layer of layer of nanomaterial is formed in composite material surface；
The mass ratio of the CNT and the composite after the cooling is 0.1:100；
The thickness of layer of nanomaterial is 10nm.
Embodiment 7
The cathode material for lithium-ion power battery of the present embodiment is the composite wood after the middle cooling of step 3) in example 2
Expect made from one layer of layer of nanomaterial of outer cladding, to concretely comprise the following steps：
Carbon nano-fiber is mixed with the composite after being cooled down in the step 3) of embodiment 2, adds water, using ultrasonic vibration point
Uniform, 150 DEG C of spray drying are dissipated, in composite material surface one layer of layer of nanomaterial of formation；
The mass ratio of the carbon nano-fiber and the composite after the cooling is 3:100；
The thickness of layer of nanomaterial is 400nm.
Embodiment 8
The cathode material for lithium-ion power battery of the present embodiment is the composite wood after the middle cooling of step 2) in embodiment 3
Expect made from one layer of layer of nanomaterial of outer cladding, to concretely comprise the following steps：
Graphene is mixed with the composite after being cooled down in the step 2) of embodiment 3, adds water, it is scattered equal using ultrasonic vibration
It is even, 150 DEG C of spray drying, one layer of layer of nanomaterial is formed in composite material surface；
The mass ratio of the graphene and the composite after the cooling is 0.5:100；
The thickness of layer of nanomaterial is 50nm.
Embodiment 9
The cathode material for lithium-ion power battery of the present embodiment is the composite wood after the middle cooling of step 3) in example 4
Expect made from one layer of layer of nanomaterial of outer cladding, to concretely comprise the following steps：
CNT is mixed with the composite after being cooled down in the step 3) of embodiment 4, adds water, is disperseed using ultrasonic vibration
Uniformly, 150 DEG C of spray drying, one layer of layer of nanomaterial is formed in composite material surface；
The mass ratio of the CNT and the composite after the cooling is 1:100；
The thickness of layer of nanomaterial is 100nm.
Embodiment 10
The cathode material for lithium-ion power battery of the present embodiment is the composite wood after being cooled down in embodiment 5 in step 3)
Expect made from one layer of layer of nanomaterial of outer cladding, to concretely comprise the following steps：
Graphene is mixed with the composite after being cooled down in the step 3) of embodiment 5, adds water, it is scattered equal using ultrasonic vibration
It is even, 150 DEG C of spray drying, one layer of layer of nanomaterial is formed in composite material surface；
The mass ratio of the graphene and the composite after the cooling is 2:100；
The thickness of layer of nanomaterial is 200nm.
Test example
By the cathode material for lithium-ion power battery in embodiment 1-10, tested in accordance with the following steps：
1) test of reversible specific capacity and first charge-discharge efficiency：
Take 96g cathode material for lithium-ion power batteries, 2.5g SBR, 1.5g CMC, add appropriate pure water and disperse
After agent is well mixed, negative pole is made；Using lithium as to electrode, 1mol/L LiPF6Solution (solvent EC, DMC, EMC, wherein
EC：DMC：EMC=1：1：1, v/v) it is electrolyte, microporous polypropylene membrane is barrier film, is assembled into simulated battery.
By the simulated battery with 0.5mA/cm2Current density carry out constant current charge-discharge experiment, charging/discharging voltage be 0~
2.0 volts, test the reversible specific capacity and first charge-discharge efficiency of negative material.Test result is as shown in table 1.
2) cycle performance is tested：
Negative pole using in step 1) is as negative pole, with LiCoO2For positive pole, 1mol/L LiPF6Solution (solvent EC,
DMC, EMC, wherein EC：DMC：EMC=1：1：1, v/v) it is electrolyte, microporous polypropylene membrane is barrier film, is assembled into resultant battery.
Charge and discharge electric test is carried out with 1C multiplying power, charging/discharging voltage is limited to 4.2~3.0V, test circulating battery 2000 times
Capability retention C2000/C1.Test result is as shown in table 1.
3) high rate performance is tested
The simulated battery that will be obtained in step 1), tests high rate performance in accordance with the following steps：
Charging/discharging voltage is limited in 0.005~2.0 volt, with 0.5mA/cm2The current density of (0.2C) carries out constant current charge and discharge
Electricity experiment, measures 0.2C discharge capacities.Fast charging and discharging performance evaluation uses 0.5mA/cm2Constant current charge, then with
5.0mA/cm2The discharge current electric discharge of (2.0C), tests 2.0C discharge capacities, calculates 2.0C discharge capacities/0.2C discharge capacities
(%).Test result is as shown in table 1.
Cathode material for lithium-ion power battery test result in the embodiment 1-10 of table 1
As shown in Table 1, negative material of the invention has excellent a high rate performance and cyclical stability, negative material can
Inverse specific capacity is more than 368mAh/g, circulates coulombic efficiency first and is more than 94%, circulates 2000 capability retentions and is more than 80%.
Claims (6)
1. a kind of preparation method of cathode material for lithium-ion power battery, it is characterised in that comprise the following steps：
1）Graphite material or carbonaceous mesophase spherules or asphalt pyrolysis carbon are added in the dopant aqueous solution, temperature is 10-80 DEG C, leaching
Stain 5-60h, filter, drying, obtain doping presoma；
The graphite material is one kind in native graphite, Delanium；
The dopant is water soluble lithium compounds or water soluble lithium compounds and water-soluble transition metal salt；
When dopant is water soluble lithium compounds, the mass percent concentration of the dopant aqueous solution is 0.1-10%, water-soluble lithiumation
Compound is 0.1-10 with graphite material or the mass ratio of carbonaceous mesophase spherules or asphalt pyrolysis carbon:100；
When dopant is water soluble lithium compounds and water-soluble transition metal salt, water soluble lithium compounds in the dopant aqueous solution
Mass percent concentration is 0.1-10%, and the concentration of water-soluble transition metal salt is 0.2-8%, water soluble lithium compounds, water solubility
Transition metal salt and the mass ratio of graphite material or carbonaceous mesophase spherules or asphalt pyrolysis carbon are 0.1-10: 0.2-8：100；
2）By step 1）Obtained doping presoma mixes with cladding carbon source, under protective atmosphere, 800-2800 DEG C of insulation 2-
20h, composite is obtained, cool down, produce cathode material for lithium-ion power battery；
The cladding carbon source and the mass ratio of the doping presoma are 0.5-20:100；
The step 2）Composite after middle cooling passes through nano-carbon material modification, the nano-carbon material modification
The step of include：
By nano-carbon material and the step 2）Composite mixing after middle cooling, adds water, is uniformly dispersed, then in 100-
250 DEG C of spray drying, composite material surface after the cooling period form one layer of layer of nanomaterial；
The nano-carbon material with the step 2）The mass ratio of composite after middle cooling is 0.1-3.0:100.
2. the preparation method of cathode material for lithium-ion power battery as claimed in claim 1, it is characterised in that the nanometer
Carbon material is any one in CNT, carbon nano-fiber, graphene.
3. the preparation method of cathode material for lithium-ion power battery as claimed in claim 1, it is characterised in that described water-soluble
Property lithium compound be lithium nitrate, lithium chloride, lithium hydroxide, any one in lithium acetate.
4. the preparation method of cathode material for lithium-ion power battery as claimed in claim 1, it is characterised in that described water
Transition metal is any one of Ag, Cu, Cr, Fe, Co, Ni, V, Mo, Sn in dissolubility transition metal salt.
5. the preparation method of cathode material for lithium-ion power battery as claimed in claim 1, it is characterised in that the cladding
Carbon source is water soluble polymer or oil-soluble macromolecule, and the water soluble polymer is polyvinyl alcohol, butadiene-styrene rubber breast SBR, carboxylic
One kind in methylcellulose CMC, the oil-soluble macromolecule be polystyrene, polymethyl methacrylate, polytetrafluoroethylene (PTFE),
One kind in Kynoar, polyacrylonitrile.
6. the preparation method of cathode material for lithium-ion power battery as claimed in claim 1, it is characterised in that the step
2）The method of middle mixing is liquid phase coating or melting cladding or solid phase cladding.
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| CN109546099B (en) * | 2018-10-16 | 2021-08-31 | 中航锂电（洛阳）有限公司 | Graphite composite negative electrode material, preparation method thereof and lithium ion battery |
| CN111354925B (en) * | 2018-12-21 | 2021-04-20 | 浙江伏打科技有限公司 | Synthesis of carbon-bound lithium ion conductor-carbon composite negative electrode material with carbon fiber structure |
| CN109786854B (en) * | 2018-12-30 | 2022-04-22 | 广州力柏能源科技有限公司 | Quick-charging lithium ion battery and preparation method thereof |
| CN112645300B (en) * | 2019-11-07 | 2023-02-07 | 上海杉杉科技有限公司 | Hard carbon negative electrode material, lithium ion battery, and preparation method and application of hard carbon negative electrode material |
| CN114314578B (en) * | 2021-04-28 | 2023-01-24 | 江西力能新能源科技有限公司 | Manufacturing process of graphene-containing negative electrode material, graphene-containing negative electrode material and lithium ion battery |
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| CN1697215A (en) * | 2005-05-27 | 2005-11-16 | 深圳市贝特瑞电子材料有限公司 | Cathode material of composite carbon in use for lithium ion battery and preparation method |
| CN103094528A (en) * | 2013-01-09 | 2013-05-08 | 深圳市贝特瑞新能源材料股份有限公司 | Hard carbon cathode material for lithium ion power and energy storage battery and preparation method of hard carbon cathode material |
| CN104332616A (en) * | 2014-09-09 | 2015-02-04 | 刘剑洪 | Graphene coated graphite composite lithium ion battery negative material and its preparation method |
| CN104393235A (en) * | 2014-04-21 | 2015-03-04 | 天津锦美碳材科技发展有限公司 | Lithium-salt-modified lithium ion battery anode material and preparation method thereof |
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| CN103094528A (en) * | 2013-01-09 | 2013-05-08 | 深圳市贝特瑞新能源材料股份有限公司 | Hard carbon cathode material for lithium ion power and energy storage battery and preparation method of hard carbon cathode material |
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