CN105161725A - Preparation method of anode material for lithium-ion power battery - Google Patents
Preparation method of anode 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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- 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
Abstract
The invention relates to a preparation method of an anode material for a lithium-ion power battery, and belongs to the technical field of lithium ion batteries. The method comprises the following steps: (1) adding a graphite material or mesocarbon microbeads or asphalt pyrolytic carbon to a dopant solution, wherein the temperature is 10-80 DEG C, dipping the graphite material or the mesocarbon microbeads or the asphalt pyrolytic carbon for 5-60 DEG C, filtering and baking the graphite material or the mesocarbon microbeads or the asphalt pyrolytic carbon to obtain a doped precursor, wherein a dopant is a water-soluble lithium compound or the water-soluble lithium compound and a transition metal salt; and (2) mixing the doped precursor prepared from the step (1) with a coated-carbon source evenly, carrying out heat preservation at 800-2800 DEG C for 2-20 hours in protective atmosphere, and cooling the mixture to obtain the anode material. The mass ratio of the coated-carbon source to the doped precursor is (0.5-20) to 100. According to the preparation method of the anode material for the lithium-ion power battery provided by the invention, the conductivity of the anode material is improved; the irreversible lithium loss is reduced; and the specific capacity and the cycle performance of the anode material are improved.
Description
Technical field
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.
Background technology
Along with development of world economy, the problem such as energy shortage, environmental pollution becomes increasingly conspicuous, and renewable, free of contamination new energy technology more and more receives publicity, and high-efficiency energy-storage device is exactly wherein a kind of.In high-efficiency energy-storage device, lithium ion battery becomes one of following 10 ~ 20 years high-efficiency energy-storage devices the most potential with advantages such as its high-energy-density, high voltage, long circulation life, pollution-free, memory-less effects.
Along with the continuous expansion of lithium ion battery applications scope, the performance requirement of different application field to lithium ion battery is also more and more higher.In the factors affecting performance of lithium ion battery, the performance of electrode material to lithium ion battery plays conclusive effect.The research of positive electrode aspect conventional at present makes the performance of the positive electrode commonly used constantly promote and moves closer to its limit, and the specific capacity of multiple positive electrode is close to its theoretical capacity, and the space of continuing to promote constantly is reduced.Given this, the raising of anticathode material property just seems more meaningful.In numerous negative materials, graphitized carbon material, owing to having good layer structure, is very suitable for embedding and the deintercalation of lithium ion, and between the graphite-lithium layer of formation, compound L i-GIC has very high specific capacity, close to LiC
6theoretical specific capacity 372mAh/g; Also there is good charging/discharging voltage platform and lower doff lithium current potential simultaneously, with conventional positive electrode, as LiCoO
2, LiMn
2o
4better etc. matching, the battery average voltage formed is high, and steadily, therefore commercial lithium-ion batteries adopts graphite-like material with carbon element as negative material in a large number at present in electric discharge.
But, the shortcoming of graphite material also clearly, the first, graphite material is high due to degree of graphitization, has height-oriented graphite laminate structure, poor with the compatibility of organic solvent, when first charge-discharge, can there is the common embedding of graphite layers in lithium and organic solvent, causes that graphite linings is peeled off, graphite granule bursts apart and efflorescence, cause electrode structure to destroy, the cycle performance of battery reduces.The second, the laminated structure due to graphite only allows lithium ion embed along the border of graphite crystal and deviate from, and response area is little, and the evolving path is long, is generally not suitable for high current charge-discharge, limits the development of lithium ion battery in fields such as electrokinetic cells.3rd, the sheet-like particle with large draw ratio is easily formed in the crushing process of graphite cathode material when prepared by powder, easily formed in the nipping process of sheet-like particle when prepared by electrode and be parallel to aligning of collector, in repeated charge process, lithium ion enters and deviates from graphite crystal inside and the c-axis direction of graphite can be caused to produce comparatively large sstrain, cause electrode structure to destroy, have impact on cycle performance; The resistance increasing that the result that exfoliated graphite particles aligns also can cause lithium ion to enter from the side of graphite crystal and deviate from, makes its fast charging and discharging performance be deteriorated.4th, due to graphite crystal and spherical and that blocky graphite Particle Phase is larger than the having specific area of sheet-like particle, easily cause lithium ion that irreversible embedding occurs, cause lithium ion battery negative material to have larger irreversible capacity in first charge-discharge process.
In order to improve the combination property of graphite material, more common method carries out modification to graphite material, as doping and coated.Publication number is the preparation method that the Chinese invention patent (publication date is on November 16th, 2005) of CN1697215A discloses a kind of cathode material of composite carbon in use for lithium ion battery, specifically discloses its preparation method and comprises the steps such as pulverizing, spheroidization process, purification process, washing, multivalent state transition metal salt solution dipping, Coated with Organic Matter, carbonization.The negative material that the method obtains has good removal lithium embedded ability and cyclical stability.But above-mentioned negative material specific capacity is lower, and cycle performance still has much room for improvement.
Summary of the invention
The object of the present invention is to provide that a kind of specific capacity is high, the preparation method of the cathode material for lithium-ion power battery of good cycle.
In order to realize above object, the technical scheme of the preparation method of cathode material for lithium-ion power battery of the present invention is as follows:
A preparation method for cathode material for lithium-ion power battery, comprises the steps:
1) add in the dopant aqueous solution by graphite material or carbonaceous mesophase spherules or asphalt pyrolysis carbon, temperature is 10-80 DEG C, and dipping 5-60h, filters, and dries, obtains doping presoma;
Described graphite material is the one in native graphite, Delanium;
Described 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%, and the mass ratio of water soluble lithium compounds and graphite material or carbonaceous mesophase spherules or asphalt pyrolysis carbon is 0.1-10:100;
Dopant be water soluble lithium compounds and water-soluble transition metal salt time, in the dopant aqueous solution, the mass percent concentration of water soluble lithium compounds is 0.1-10%, the concentration of water-soluble transition metal salt is 0.2-8%, and the mass ratio of water soluble lithium compounds, water-soluble transition metal salt and graphite material or carbonaceous mesophase spherules or asphalt pyrolysis carbon is 0.1-10:0.2-8:100;
2) by step 1) obtained doping presoma mix with coated carbon source, and under protective atmosphere, 800-2800 DEG C is incubated 2-20h, obtains composite material, cools, obtains cathode material for lithium-ion power battery;
The mass ratio of described coated carbon source and described doping presoma is 0.5-20:100.
Graphite material or carbonaceous mesophase spherules or asphalt pyrolysis carbon flood by the preparation method of cathode material for lithium-ion power battery of the present invention in the dopant solution of water soluble lithium compounds or water soluble lithium compounds and transition metal salt, when dopant is water soluble lithium compounds, dipping can in graphite material or carbonaceous mesophase spherules or asphalt pyrolysis carbon elements doped lithium, a certain amount of extra lithium can be provided for negative material, the irreversible lithium loss of graphite material or carbonaceous mesophase spherules or asphalt pyrolysis carbon when supplementing discharge and recharge, improve the capacity of negative material on the whole.When dopant comprises water soluble lithium compounds and transition metal salt simultaneously, after transition metal participation electrode reaction, the lithium of a part can be fixed, cause certain irreversible lithium loss, lithium compound can provide extra lithium, supplement the lithium loss that transition metal causes, act synergistically with transition metal, common specific capacity and the structural stability improving negative material.
Described step 2) in cooled composite material through nano-carbon material modification, the step of described nano-carbon material modification comprises:
By nano-carbon material and described step 2) in cooled composite material mix, described be mixed into solid phase mixing or liquid phase mixing, add water, adopt ultrasonic vibration be uniformly dispersed, then at 100-250 DEG C of spraying dry, composite material surface after the cooling period forms one deck layer of nanomaterial;
Described nano-carbon material with described step 2) in the mass ratio of cooled composite material be 0.1-3.0:100.
Above-mentioned nano-carbon material can reduce the change in volume amplitude of graphite material or carbonaceous mesophase spherules or asphalt pyrolysis carbon in charge and discharge process, is conducive to the Stability Analysis of Structures keeping negative material, improves its cycle performance.In addition, nano-carbon material material has stronger conductivity, is conducive to the multiplying power discharging property improving negative material.
Described nano-carbon material is the one in carbon nano-tube, carbon nano-fiber, Graphene.These nano-carbon materials form the network configuration of intersecting at graphite material or carbonaceous mesophase spherules or asphalt pyrolysis carbon surface, self have stronger toughness, further enhancing the structural stability of material.
The impedance that the thickness of layer of nanomaterial is excessive when easily causing Lithium-ion embeding and deviate from increases, be unfavorable for high rate charge-discharge, the thickness of layer of nanomaterial too small then again can more weak its to the inhibitory action of graphite material or carbonaceous mesophase spherules or the distortion of asphalt pyrolysis carbon, general, the thickness of described 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 be convenient to doping and coated, described graphite material or carbonaceous mesophase spherules or asphalt pyrolysis carbon are through pulverizing, spheroidization process.
In order to avoid impurity is on the impact of coated process, described graphite material or carbonaceous mesophase spherules or asphalt pyrolysis carbon are through purification process.
Described purification process gets graphite material or carbonaceous mesophase spherules or asphalt pyrolysis carbon, jointly join in reactor with oxidant, add water and be uniformly mixed 5-15min, stirring and refluxing 1-20h at the temperature of 50-360 DEG C, add complexing agent again and carry out complex reaction, the complex reaction time is 2-10h.Add water washing 10 ~ 60min after complex reaction, then carry out centrifugal dehydration, then be less than 0.2% 100 ~ 360 DEG C of oven dry to moistures.The each individual event content of material medium trace element Fe, Cu, Cr, Na, Ca, Zn, Mn, Al, Si that purification process obtains all is less than 50ppm, and the summation of above-mentioned micronutrient levels is less than 150ppm.
The oxidant that above-mentioned purification process adopts is the mixture of any two or three in hydrogen peroxide, Peracetic acid, chlorine dioxide, chlorine, NaOH, the concentrated sulfuric acid, nitric acid, concentrated hydrochloric acid, perchloric acid.
The complexing agent that above-mentioned purification process adopts is the one in nitrilotriacetic acid, ferric trichloride, hydrofluoric acid, phosphoric acid, hydrochloric acid or cholic acid complexing agent.
Be washed with water to neutrality after purification process, dry.
Water soluble lithium compounds is preferably the one in lithium nitrate, lithium chloride, lithium hydroxide, lithium acetate.
In described water-soluble transition metal salt, transition metal is the one of Ag, Cu, Cr, Fe, Co, Ni, V, Mo, Sn.
Described coated carbon source is water soluble polymer or oil-soluble macromolecule, described water soluble polymer is the one in polyvinyl alcohol, butadiene-styrene rubber breast SBR, carboxyl methyl cellulose, and described oil-soluble macromolecule is the one in polystyrene, polymethyl methacrylate, polytetrafluoroethylene, Kynoar, polyacrylonitrile.
Described step 2) in the method for mixing be liquid phase coating or melting is coated or solid phase is coated.
The negative material that the preparation method of cathode material for lithium-ion power battery of the present invention obtains, by adding lithium compound and transition metal in core material with carbon element, improve the conductivity of negative material, and decrease the loss of irreversible lithium, improve specific capacity and the cycle performance of negative material.Its reversible specific capacity is greater than 368mAh/g, and circulation coulombic efficiency is greater than 94% first, and 2000 capability retentions that circulate are greater than 80%.There is excellent lithium storage performance, and preparation cost is cheap, is suitable as each type electric tool, lithium ion battery for electric vehicle negative material.
Embodiment
Below in conjunction with specific embodiment, technical scheme of the present invention is further detailed.
Embodiment 1
The preparation method of the cathode material for lithium-ion power battery of the present embodiment comprises the steps:
1) preliminary treatment
A. pulverize: native graphite is added in high speed disintegrator, pulverize 30min under the rotating speed of 2000rpm and obtain graphite powder; The particle diameter of described native graphite is 75 μm;
B. spheroidization process: joined by the graphite powder obtained in low velocity impact formula nodularization pulverizer, carries out shaping and spheroidization process 240min, obtains spheroidization graphite under 500rpm rotating speed;
C. purification process: the spheroidization graphite obtained in 100kg step B is put into reactor, adds the mixed acid 35kg of sulfuric acid and nitric acid, adds suitable quantity of water, stir 10min, stirring and refluxing 18h at the temperature of 300 DEG C, then add ferric trichloride 15kg, add water and stir into pasty state, reaction 2h; Add water washing 10min, then carry out centrifugal dehydration, then be less than 0.2% 100 DEG C of oven dry to moisture, obtain dry graphite powder;
2) adulterate precursor power
By step 1) in the dry graphite powder that obtains add in dopant solution, flood 5h at 25 DEG C, filter, dehydration, dry, obtain doping presoma;
Described dopant is lithium nitrate and silver nitrate, and dopant solution is the aqueous solution of lithium nitrate and silver nitrate, and wherein the concentration of lithium nitrate is 5%, and the concentration of silver nitrate is 1.7%;
Dopant with the mass ratio of dry graphite powder is: lithium nitrate: silver nitrate: dry graphite powder=5:1.7:100;
3) coated
By step 2) in the doping presoma that obtains add mixing in butadiene-styrene rubber (SBR), add water and be uniformly dispersed, at 150 DEG C, carry out spraying dry, under nitrogen protection, be warming up to 1000 DEG C with the programming rate of 0.5 DEG C/min, insulation 2h, obtain composite material, be cooled to room temperature, broken, screening, to obtain final product;
The mass ratio of doping 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 steps:
1) preliminary treatment
A. pulverize: Delanium is added in high speed disintegrator, pulverize 120min under the rotating speed of 5000rpm and obtain graphite powder; The particle diameter of described native graphite is 1000 μm;
B. spheroidization process: joined by the graphite powder obtained in low velocity impact formula nodularization pulverizer, carries out shaping and spheroidization process 60min, obtains spheroidization graphite under 2000rpm rotating speed;
C. purification process: the spheroidization graphite obtained in 100kg step B is put into reactor, adds the mixture 35kg of hydrogen peroxide and Peracetic acid, adds suitable quantity of water, stir 5min, stirring and refluxing 12h at the temperature of 100 DEG C, then add ferric trichloride 15kg, add water and stir into pasty state, reaction 10h; Add water washing 60min, then carry out centrifugal dehydration, then be less than 0.2% 360 DEG C of oven dry to moisture, obtain dry graphite powder;
2) adulterate precursor power
By step 1) in the dry graphite powder that obtains add in dopant solution, flood 10h at 80 DEG C, filter, dehydration, dry, obtain doping presoma;
Described dopant is lithium hydroxide and copper nitrate, and dopant solution is the aqueous solution of lithium hydroxide and copper nitrate, and wherein the concentration of lithium hydroxide is 0.1%, and the concentration of silver nitrate is 0.2%;
Dopant with the mass ratio of dry graphite powder is: lithium hydroxide: copper nitrate: dry graphite powder=0.1:0.2:100;
3) coated
By step 2) in the doping presoma that obtains add in the polyvinyl alcohol of melting and mix, under nitrogen protection, be warming up to 2800 DEG C with the programming rate of 20 DEG C/min, insulation 2h, obtains composite material, is cooled to room temperature, broken, and screening, to obtain final product;
The mass ratio of doping 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 steps:
1) adulterate precursor power
The carbonaceous mesophase spherules powder of drying is added in dopant solution, at 20 DEG C, floods 60h, filter, dehydration, dry, obtain doping presoma;
Described dopant is lithium chloride and nitric acid nickel (NO
3)
2, dopant solution is the aqueous solution of lithium chloride and nickel nitrate, and wherein the concentration of lithium chloride is 4.5%, and the concentration of nickel nitrate is 5.0%;
Dopant with the mass ratio of dry carbonaceous mesophase spherules powder is: lithium chloride: nickel nitrate: dry carbonaceous mesophase spherules powder=4.5:5:100;
2) coated
By step 2) in the doping presoma that obtains mix with carboxyl methyl cellulose, under nitrogen protection, be warming up to 800 DEG C with the programming rate of 1 DEG C/min, insulation 20h, obtains composite material, is cooled to room temperature, broken, and screening, to obtain final product;
The mass ratio of doping 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 steps:
1) preliminary treatment
A. pulverize: asphalt pyrolysis carbon is added in high speed disintegrator, pulverizes 60min under the rotating speed of 4000rpm and obtain asphalt pyrolysis carbon dust; The particle diameter of described asphalt pyrolysis carbon is 200 μm;
B. spheroidization process: joined by the asphalt pyrolysis carbon dust obtained in low velocity impact formula nodularization pulverizer, carries out shaping and spheroidization process 180min, obtains spheroidization asphalt pyrolysis carbon dust under 1200rpm rotating speed;
C. purification process: the spheroidization asphalt pyrolysis carbon dust obtained in 100kg step B is put into reactor, adds the mixture 35kg of sulfuric acid and nitric acid, add suitable quantity of water, stir 15min, stirring and refluxing 2h at the temperature of 200 DEG C, then add nitrilotriacetic acid 15kg, add water and stir into pasty state, reaction 4h; Add water washing 30min, then carry out centrifugal dehydration, then be less than 0.2% 200 DEG C of oven dry to moisture, obtain dry asphalt pyrolysis carbon dust;
2) adulterate precursor power
By step 1) in the asphalt pyrolysis carbon dust of drying that obtains add in dopant solution, flood 50h at 30 DEG C, filter, dehydration, dry, obtain doping presoma;
Described dopant is lithium acetate and chromic nitrate Cr (NO
3)
3, dopant solution is the aqueous solution of lithium acetate and chromic nitrate, and wherein the concentration of lithium acetate is 10%, and the concentration of chromic nitrate is 8.0%;
Dopant with the mass ratio of dry asphalt pyrolysis carbon dust is: lithium acetate: chromic nitrate: dry asphalt pyrolysis carbon dust=10:8:100;
3) coated
By step 2) in the doping presoma that obtains add in the toluene solution of polystyrene and mix, solvent evaporated, adds water and is uniformly dispersed, and carries out spraying dry at 150 DEG C, under nitrogen protection, be warming up to 1200 DEG C with the programming rate of 5 DEG C/min, insulation 10h, obtains composite material, be cooled to room temperature, fragmentation, screening, to obtain final product;
The mass ratio of doping 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 steps:
1) preliminary treatment
A. pulverize: native graphite is added in high speed disintegrator, pulverize 30min under the rotating speed of 2000rpm and obtain graphite powder; The particle diameter of described asphalt pyrolysis carbon is 75 μm;
B. spheroidization process: joined by the graphite powder obtained in low velocity impact formula nodularization pulverizer, carries out shaping and spheroidization process 240min, obtains spheroidization graphite under 500rpm rotating speed;
C. purification process: the spheroidization graphite obtained in 100kg step B is put into reactor, adds the mixture 35kg of sulfuric acid and nitric acid, adds suitable quantity of water, stir 10min, stirring and refluxing 18h at the temperature of 80 DEG C, then add nitrilotriacetic acid 15kg, add water and stir into pasty state, reaction 2h; Add water washing 30min, then carry out centrifugal dehydration, then be less than 0.2% 200 DEG C of oven dry to moisture, obtain dry graphite powder;
2) adulterate precursor power
By step 1) in the dry graphite powder that obtains add in dopant solution, flood 5h at 25 DEG C, filter, dehydration, dry, obtain doping presoma;
Described dopant is lithium nitrate, and dopant solution is the aqueous solution of lithium nitrate, and wherein the concentration of lithium nitrate is 5%;
Dopant with the mass ratio of dry graphite powder is: lithium nitrate: dry graphite powder=5:100;
3) coated
By step 2) in the doping presoma that obtains add in butadiene-styrene rubber and mix, add water and be uniformly dispersed, carry out spraying dry at 150 DEG C, under nitrogen protection, be warming up to 1000 DEG C with the programming rate of 0.5 DEG C/min, insulation 12h, obtains composite material, is cooled to room temperature, fragmentation, screening, to obtain final product;
The mass ratio of doping presoma and butadiene-styrene rubber is 100:1.5.
Embodiment 6
The cathode material for lithium-ion power battery of the present embodiment is step 3 in embodiment 1) in cooled composite material outer cladding one deck layer of nanomaterial obtain, concrete steps are:
By carbon nano-tube and embodiment 1 step 3) in cooled composite material mix, add water, adopt ultrasonic vibration be uniformly dispersed, 150 DEG C of spraying dry, form one deck layer of nanomaterial at composite material surface;
The mass ratio of described carbon nano-tube and described cooled composite material 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 step 3 in example 2) in cooled composite material outer cladding one deck layer of nanomaterial obtain, concrete steps are:
By carbon nano-fiber and embodiment 2 step 3) in cooled composite material mix, add water, adopt ultrasonic vibration be uniformly dispersed, 150 DEG C of spraying dry, form one deck layer of nanomaterial at composite material surface;
The mass ratio of described carbon nano-fiber and described cooled composite material 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 step 2 in embodiment 3) in cooled composite material outer cladding one deck layer of nanomaterial obtain, concrete steps are:
By Graphene and embodiment 3 step 2) in cooled composite material mix, add water, adopt ultrasonic vibration be uniformly dispersed, 150 DEG C of spraying dry, form one deck layer of nanomaterial at composite material surface;
The mass ratio of described Graphene and described cooled composite material 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 step 3 in example 4) in cooled composite material outer cladding one deck layer of nanomaterial obtain, concrete steps are:
By carbon nano-tube and embodiment 4 step 3) in cooled composite material mix, add water, adopt ultrasonic vibration be uniformly dispersed, 150 DEG C of spraying dry, form one deck layer of nanomaterial at composite material surface;
The mass ratio of described carbon nano-tube and described cooled composite material is 1:100;
The thickness of layer of nanomaterial is 100nm.
Embodiment 10
Cathode material for lithium-ion power battery step 3 in embodiment 5 of the present embodiment) in cooled composite material outer cladding one deck layer of nanomaterial obtain, concrete steps are:
By Graphene and embodiment 5 step 3) in cooled composite material mix, add water, adopt ultrasonic vibration be uniformly dispersed, 150 DEG C of spraying dry, form one deck layer of nanomaterial at composite material surface;
The mass ratio of described Graphene and described cooled composite material 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, test in accordance with the following steps:
1) test of reversible specific capacity and first charge-discharge efficiency:
Get the CMC of SBR, 1.5g of 96g cathode material for lithium-ion power battery, 2.5g, add appropriate pure water dispersant evenly after, make negative pole; Be to electrode with lithium, the LiPF of 1mol/L
6solution (solvent is EC, DMC, EMC, wherein EC:DMC:EMC=1:1:1, v/v) be electrolyte, microporous polypropylene membrane is barrier film, is assembled into simulated battery.
By this simulated battery with 0.5mA/cm
2current density carry out constant current charge-discharge experiment, charging/discharging voltage is 0 ~ 2.0 volt, the test reversible specific capacity of negative material and first charge-discharge efficiency.Test result is as shown in table 1.
2) cycle performance test:
Using step 1) in negative pole as negative pole, with LiCoO
2for positive pole, the LiPF of 1mol/L
6solution (solvent is EC, DMC, EMC, wherein EC:DMC:EMC=1:1:1, v/v) be electrolyte, microporous polypropylene membrane is barrier film, is assembled into resultant battery.
Carry out discharge and recharge test with the multiplying power of 1C, charging/discharging voltage is restricted to 4.2 ~ 3.0V, and test battery circulates the capability retention C of 2000 times
2000/ C
1.Test result is as shown in table 1.
3) high rate performance test
By step 1) in the simulated battery that obtains, test high rate performance in accordance with the following steps:
Charging/discharging voltage is limited in 0.005 ~ 2.0 volt, with 0.5mA/cm
2(0.2C) current density carries out constant current charge-discharge experiment, records 0.2C discharge capacity.Fast charging and discharging performance evaluation adopts 0.5mA/cm
2constant current charge, then with 5.0mA/cm
2(2.0C) discharging current electric discharge, test 2.0C discharge capacity, calculates 2.0C discharge capacity/0.2C discharge capacity (%).Test result is as shown in table 1.
Cathode material for lithium-ion power battery test result in table 1 embodiment 1-10
As shown in Table 1, negative material of the present invention has excellent high rate performance and cyclical stability, and the reversible specific capacity of negative material is greater than 368mAh/g, and circulation coulombic efficiency is greater than 94% first, and 2000 capability retentions that circulate are greater than 80%.
Claims (7)
1. a preparation method for cathode material for lithium-ion power battery, is characterized in that, comprises the steps:
1) add in the dopant aqueous solution by graphite material or carbonaceous mesophase spherules or asphalt pyrolysis carbon, temperature is 10-80 DEG C, and dipping 5-60h, filters, and dries, obtains doping presoma;
Described graphite material is the one in native graphite, Delanium;
Described 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%, and the mass ratio of water soluble lithium compounds and graphite material or carbonaceous mesophase spherules or asphalt pyrolysis carbon is 0.1-10:100;
Dopant be water soluble lithium compounds and water-soluble transition metal salt time, in the dopant aqueous solution, the mass percent concentration of water soluble lithium compounds is 0.1-10%, the concentration of water-soluble transition metal salt is 0.2-8%, and the mass ratio of water soluble lithium compounds, water-soluble transition metal salt and graphite material or carbonaceous mesophase spherules or asphalt pyrolysis carbon is 0.1-10:0.2-8:100;
2) by step 1) obtained doping presoma mix with coated carbon source, and under protective atmosphere, 800-2800 DEG C is incubated 2-20h, obtains composite material, cools, obtains cathode material for lithium-ion power battery;
The mass ratio of described coated carbon source and described doping presoma is 0.5-20:100.
2. the preparation method of cathode material for lithium-ion power battery as claimed in claim 1, is characterized in that, described step 2) in cooled composite material through nano-carbon material modification, the step of described nano-carbon material modification comprises:
By nano-carbon material and described step 2) in cooled composite material mix, add water, be uniformly dispersed, then at 100-250 DEG C of spraying dry, composite material surface after the cooling period forms one deck layer of nanomaterial;
Described nano-carbon material with described step 2) in the mass ratio of cooled composite material be 0.1-3.0:100.
3. the preparation method of cathode material for lithium-ion power battery as claimed in claim 2, is characterized in that, described nano-carbon material is any one in carbon nano-tube, carbon nano-fiber, Graphene.
4. the preparation method of cathode material for lithium-ion power battery as claimed in claim 1, is characterized in that, described water soluble lithium compounds is any one in lithium nitrate, lithium chloride, lithium hydroxide, lithium acetate.
5. the preparation method of cathode material for lithium-ion power battery as claimed in claim 1, it is characterized in that, in described water-soluble transition metal salt, transition metal is any one of Ag, Cu, Cr, Fe, Co, Ni, V, Mo, Sn.
6. the preparation method of cathode material for lithium-ion power battery as claimed in claim 1, it is characterized in that, described coated carbon source is water soluble polymer or oil-soluble macromolecule, described water soluble polymer is the one in polyvinyl alcohol, butadiene-styrene rubber breast SBR, carboxyl methyl cellulose, and described oil-soluble macromolecule is the one in polystyrene, polymethyl methacrylate, polytetrafluoroethylene, Kynoar, polyacrylonitrile.
7. the preparation method of cathode material for lithium-ion power battery as claimed in claim 1, is characterized in that, described step 2) in the method for mixing be liquid phase coating or melting is coated or solid phase is coated.
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