CN104505491B - Natural graphite negative electrode material method of modifying and composite - Google Patents
Natural graphite negative electrode material method of modifying and composite Download PDFInfo
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- CN104505491B CN104505491B CN201410794705.5A CN201410794705A CN104505491B CN 104505491 B CN104505491 B CN 104505491B CN 201410794705 A CN201410794705 A CN 201410794705A CN 104505491 B CN104505491 B CN 104505491B
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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- 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 discloses a kind of natural graphite negative electrode material method of modifying and composite, high-rate charge-discharge capability and the cryogenic property being to improve natural graphite negative electrode material will be solved the technical problem that, reduce preparation cost, reduce the pollution to environment.The method of the present invention includes electrolytic oxidation, inserts metal ion, reduction, pyrolysis, cladding, sintering.The natural graphite cathode composite of the present invention, graphite matrix is coated with carbon coating layer, and the interlayer of graphite matrix is distributed metal and the alloy of nanoscale scope.The present invention is compared with prior art, adding native graphite c-axis direction electronic conductivity, the big multiplying power discharging property and cryogenic property, nano metal and the alloy that improve negative material have storage lithium ability the most by force, improve the specific discharge capacity of material, clad effectively improves electrolyte and corrodes graphite layers, it is therefore prevented that graphite flake layer comes off, and improves the cycle performance of material, preparation method is simple, it is easily controlled, low cost, it is easy to industrialized production.
Description
Technical field
The present invention relates to preparation method and the material of a kind of new energy materials, particularly a kind of lithium ion battery is multiple
Close preparation method and the material of negative material.
Background technology
Graphite is one of important cathode material of lithium ion battery, and as important strategic resource, it is with dilute
Earth elements is also referred to as " industry monosodium glutamate ".Wherein, China's native graphite accounts for more than the 70% of world saving, is state
The maximum supply country in market, border.Native graphite is used as the negative material of lithium ion battery, with organic electrolyte
Poor compatibility, easily occurs graphite flake layer to peel off, affects high rate during charging-discharging and cycle life during discharge and recharge.
And both at home and abroad for the research of natural graphite negative electrode material, currently mainly follow the thinking of surface modification, modified
Means and method specifically include that spheroidization process, surface low-level oxidation, Surface coating, surface organic and unit
Element doping etc..Although surface modification improves surface texture and the chemical property of native graphite to a certain extent,
Reduce the electrolyte corrosion to graphite synusia, be effectively increased natural graphite negative electrode material first charge-discharge effect
Rate and cycle life, but to its high rate charge-discharge performance, and the improvement effect of high temperature performance still has
Limit.
Native graphite electronic conductivity in its Graphene aspect is 0.4～2.5 × 104S·cm-1, and at interlayer
Electronic conductivity along c-axis direction is only 1～5S cm-1, interlayer electrical conductivity is far below graphene layer sheet conductance
Rate.Meanwhile, Li+Diffusion coefficient in natural graphite material is higher, and about 10-8cm2·s-1, therefore native graphite
The high rate performance of negative material depends primarily on interlayer charge transfer velocity, i.e. c-axis direction electronic conductivity.
Preferable native graphite crystal layer spacing is 0.3354nm, oxidation-treated rear graphite layers away from can increase to 0.5～
0.8nm.Polarity oxy radical hydroxyl, carboxyl and the ether that graphite layers after oxidation processes exists, can be effective
Increasing oxidation of natural graphite dissolubility in aqueous solution, this is conducive to little at layer expansion graphite sheet Intercalation reaction
Particle diameter metal ion, simultaneously the most in addition condition controls to make metal ion generation reduction reaction, and removes graphite oxide
Except surface polarity oxy radical, nano metal and alloy particle and reduction-oxidation graphite after heat treatment, can be formed
Composite.Nano metal and alloy material electrical conductivity thereof are 104～105S·cm-1, it inserts natural stone layer of ink
The electronic conductivity in c-axis direction will be dramatically increased after between, the multiplying power of natural graphite negative electrode material can be effectively improved
Charge-discharge performance.It addition, after native graphite is oxidation-treated, graphite layers away from increase can be effectively improved Li+
Diffusivity, such that it is able to improve the cryogenic property of natural graphite negative electrode material.
But, current few people study by composite modified to natural graphite negative electrode material interlayer, to improve
The high rate charge-discharge performance of negative material and cryogenic property.Korea S follow the mandate of heaven national university Lee et al. utilize
Native graphite is modified processing by the processes such as Hummer method, backflow and heat treatment, is prepared for titanium dioxide
Stannum and reduced graphene SnO2/ rGO nano composite material, successfully by nano SnO2Granule is embedded into chemical combination
In the graphene-structured of valency crosslinking.Shown by electrochemical property test, tin ash and reduced graphene
SnO2The embedding de-lithium capacity of/rGO nano-complex and multiplying power discharging property are all significantly improved.Above-mentioned side
In method, utilizing Hummer method to prepare graphite oxide, graphite layers is big away from accurately controlling difficulty, preparation cost
Higher, big for environment pollution；By nano SnO in prepared material2Granule is embedded into the stone of quantivalence crosslinking
In ink alkene structure, the layer structure that heavy damage native graphite self is orderly, graphite linings is peeled off serious, is made
The tap density of material is greatly reduced, and specific surface area increases, materials processing degradation；SnO simultaneously2Granule
Bulking effect in charge and discharge process is obvious, easily causes composite stone layer of ink and further peels off, and then impact
The cycle performance of composite.
Summary of the invention
It is an object of the invention to provide a kind of natural graphite negative electrode material method of modifying and composite, solve
Technical problem is that high-rate charge-discharge capability and the cryogenic property improving natural graphite negative electrode material, reduce system
Standby cost, reduces the pollution to environment.
The present invention is by the following technical solutions: a kind of natural graphite negative electrode material method of modifying, including following step
Rapid:
One, electrolytic oxidation, by native graphite and electrolyte 1.0:3.5 in mass ratio～5.0, puts after mixed pulp
Entering electrolysis bath, the electric current density controlled between anode and negative electrode is 10～35mA/cm2, the electrolytic oxidation time is
1.5～4.0h, make the interlamellar spacing of native graphite increase to 0.4～0.7nm, washing make its pH value to 6.5～7.0,
Filter, directly 60 DEG C of drying, obtain graphite oxide；
Two, insert metal ion, graphite oxide be configured to mass content 30～the graphite oxide aqueous solution of 70%,
Add metal ion molar concentration be 0.1～1.0mol/L can intercalation hybrid metal solion, aoxidize stone
Ink solution with can intercalation hybrid metal solion volume ratio be 3:1, be 1～5KHz in frequency, power is close
Degree is 0.30～0.45w/cm2Under conditions of, ultrasonic disperse 25～60min, obtain graphite oxide metal ion and mix
Close solution；Described can intercalation hybrid metal solion be the two or three of stannum, cobalt, nickel and manganese salt solution,
The molar concentration rate of two metal ion species is 1:1, and the molar concentration rate of three metal ion species is 1:1:1；
Three, reduction, controlling temperature is 45～85 DEG C, in supersonic frequency 0.5～2.5KHz, power density
0.25～0.35w/cm2Under the conditions of, add mass content 10～25% reductant solution to graphite oxide metal from
In sub-mixed solution, reducing agent is 2.05 with the mol ratio of metal ion in graphite oxide metallic ion mixed liquor
～2.85:1, reductant solution adds complete, continues ultrasonic disperse 40～120min, during reduction reaction
Making solution ph be maintained at 8.0～9.0, the mixed reaction solution after ultrasonic disperse terminates at room temperature stands old
Change 2～8h；Described reducing agent is hydrazine hydrate, azanol or sodium borohydride；
Four, pyrolysis, by mixed reaction solution washing to pH value 6.5～7.5, filters, and obtain after filtration consolidates
Body material is placed in high-temperature atmosphere furnace, is warming up to 180～500 DEG C with the heating rate of 3～10 DEG C/h, low temperature pyrogenation
Process 3～8h, be naturally cooling to room temperature, obtain the graphite composite material after nano metal and alloy and reduction；
Five, the graphite composite wood after cladding, preparation mass fraction 10～the nano metal of 30% and alloy and reduction
Material aqueous solution, adding quality is nano metal and alloy and graphite composite material 4～the covering of 14%, carries out
Liquid-phase mixing, rotating speed is 200～1000r/min, mechanical agitation 40～100min, is atomized pelletize, obtains natural stone
Ink anode material presoma；Described covering is more than one of Colophonium, Polyethylene Glycol and phenolic resin；
Six, sintering, heats up natural graphite cathode composite material precursor with the heating rate of 60-120 DEG C/h
To 700～1200 DEG C, sinter 8～13h, naturally cool to room temperature, obtain natural graphite cathode composite.
The quality phosphorus content of the native graphite of step one of the present invention is more than 99%, and granularity D50 is 8～23 μm.
The electrolyte of step one of the present invention is mass content 30～the phosphoric acid of 60%, nitric acid, formic acid or acetic acid.
Two or three metal ion of step 2 of the present invention is same acid group.
The pink salt of step 2 of the present invention is tin acetate, STANNOUS SULPHATE CRYSTALLINE and nitric acid stannum；Cobalt salt is cobalt acetate, cobaltous sulfate
And cobalt nitrate；Nickel salt is nickel acetate, nickel sulfate and nickel nitrate；Manganese salt is manganese acetate, manganese sulfate and manganese nitrate.
Step 3 of the present invention reduction is carried out under the protective gas atmosphere that flow is 0.15～0.45L/min；Institute
Stating step 4 pyrolysis is 0.4～1.2m at flow3Carry out under the protective gas protection of/h；Described step 6 sinters
It is 0.4～1.2m at gas flow3Carry out under the protective gas atmosphere of/h；Protective gas is nitrogen, argon
With more than one of helium.
Dripping ammonia in the former course of reaction of step 3 of the present invention makes solution ph be maintained at 8.0～9.0.
Natural graphite cathode composite material precursor is put into tablet machine and is pressed into diameter by step 6 of the present invention
The blank of 300mm × highly 200mm, pressure is 3～10MPa, and the pressed compact time is 0.5～3.0 hour.
Pulverize after step 6 of the present invention sintering.
A kind of natural graphite cathode composite, graphite matrix is coated with carbon coating layer, described graphite matrix
Interlayer metal and the alloy of nanoscale scope are distributed, nano metal and alloy mass are graphite quality
0.05～5%；The predecessor quality of described carbon coating layer is the 4 of the quality sum of nano metal and alloy and graphite
～14%；The predecessor of carbon coating layer is more than one of covering Colophonium, Polyethylene Glycol and phenolic resin；Institute
State the native graphite that graphite is quality phosphorus content more than 99%.
The present invention compared with prior art, uses electrolytic oxidation to prepare oxidation of natural graphite, it is to avoid to use strong oxygen
Agent pollutes environment, control electric current density and time can effectively control graphite layers away from, make metal ion be prone to
Embed between graphite flake layer, reduce graphite flake layer and peel off, at the nano metal that the reduction of native graphite interlayer generates
And alloy, add native graphite c-axis direction electronic conductivity, improve the big multiplying power discharging of negative material
Performance and cryogenic property, nano metal and alloy have storage lithium ability the most by force, improve the electric discharge specific volume of material
Amount, clad effectively improves electrolyte and corrodes graphite layers, it is therefore prevented that graphite flake layer comes off, and improves
The cycle performance of material, preparation method is simple, is easily controlled, low cost, it is easy to industrialized production.
Accompanying drawing explanation
Fig. 1 is the method mechanism of modification schematic diagram of the present invention.
Fig. 2 is the transmission electron microscope photo that embodiment 3 obtains natural graphite cathode matrices of composite material layer structure.
Fig. 3 is that embodiment 3 obtains the saturating of natural graphite cathode matrices of composite material interlayer nano metal and alloy
Penetrate electromicroscopic photograph.
Detailed description of the invention
It is described in further detail to the present invention with embodiment below in conjunction with the accompanying drawings.
As it is shown in figure 1, the method for modifying of the natural graphite negative electrode material of the present invention, the interlayer to native graphite
Carry out Combined Processing, at the native graphite Intercalation reaction transition metal ions of oxidation, through reduction in graphite layers
Generate metal and the granule of alloy of nanoscale scope, form interlayer " bridging connects ", due to nano metal and conjunction
The granule of gold has good electric conductivity, and metal and alloy have storage lithium ability, can effectively promote natural stone
Ink capacity and graphite layers conductivity, make natural graphite negative electrode material high rate charge-discharge performance effectively be changed
Kind.
Meanwhile, in order to suppress graphite linings in natural graphite negative electrode material charge and discharge process to be stripped, the present invention's
Method also carries out Surface coating and high-temperature heat treatment to the native graphite after interlayer Combined Processing, natural to promote
The cycle performance of graphite cathode material.
The method of modifying of the natural graphite negative electrode material of the present invention, comprises the following steps:
One, electrolytic oxidation, under room temperature (20 DEG C), by native graphite and electrolyte 1.0:3.5 in mass ratio～5.0,
Put into electrolysis bath after mixed pulp, make anode current collector with 316L rustless steel, make negative electrode with stereotype, use perseverance
Electric current density between electric current instrument control anode and negative electrode is 10～35mA/cm2, to sky in square electrolysis bath
So graphite carries out electrolytic oxidation, and the electrolytic oxidation time is 1.5～4.0h, makes the interlamellar spacing of native graphite increase to
0.4～0.7nm, then with distilled water wash aoxidize after native graphite so that it is pH value to 6.5～7.0, filter,
Directly 60 DEG C of drying, obtain graphite oxide.
The quality phosphorus content of native graphite is more than 99%, and granularity D50 is 8～23 μm.
Electrolyte is mass content 30～the phosphoric acid of 60%, nitric acid, formic acid or acetic acid.
Step one electrolytic oxidation native graphite, increase graphite layers away from, insert it for subsequent step metal ion
Middle offer passage and space.
Two, insert metal ion, graphite oxide be configured to mass content 30～the graphite oxide aqueous solution of 70%,
In ultrasonic response still, add metal ion molar concentration be 0.1～1.0mol/L can intercalation mixing gold
Belong to solion, graphite oxide aqueous solution with can intercalation hybrid metal solion volume ratio be 3:1, in frequency
Being 1～5KHz, power density is 0.30～0.45w/cm2Under conditions of, ultrasonic disperse 25～60min, obtain
Graphite oxide metallic ion mixed liquor.
Can intercalation hybrid metal solion be the two or three of stannum, cobalt, nickel and manganese salt solution, two kinds of gold
The molar concentration rate belonging to ion is 1:1, and the molar concentration rate of three metal ion species is 1:1:1, two or three gold medal
Belong to ion and be same acid group.
Pink salt is tin acetate, STANNOUS SULPHATE CRYSTALLINE and nitric acid stannum.
Cobalt salt is cobalt acetate, cobaltous sulfate and cobalt nitrate.
Nickel salt is nickel acetate, nickel sulfate and nickel nitrate.
Manganese salt is manganese acetate, manganese sulfate and manganese nitrate.
Step 2 metal ion, under the peptizaiton of ultrasonic energy, is inserted into the interlayer of graphite oxide.
Three, reduction, under normal pressure, under the protective gas atmosphere that flow is 0.15～0.45L/min, uses
Heating in water bath mode, controlling ultrasonic response still temperature is 45～85 DEG C, in supersonic frequency 0.5～2.5KHz,
Power density 0.25～0.35w/cm2Under the conditions of, be slowly added to mass content 10～25% reductant solution extremely
In the graphite oxide metallic ion mixed liquor of ultrasonic response still, reducing agent mixes with graphite oxide metal ion
The mol ratio closing metal ion in solution is 2.05～2.85:1, and reductant solution adds complete, continues ultrasonic
Dispersion 40～120min, drips ammonia and makes solution ph be maintained at 8.0～9.0 during reduction reaction, ultrasonic
Disperse the mixed reaction solution the most still aging 2～8h after terminating.
Reducing agent is hydrazine hydrate, azanol or sodium borohydride.
Protective gas is more than one of nitrogen, argon and helium.
Slowly referring to not produce splashing when adding reducing agent, solution is splashed on ultrasonic response still still wall.
Step 3 is under the peptizaiton of ultrasonic energy, and metal ion goes successively to the interlayer of graphite oxide, also
Under the peptizaiton of former dose and ultrasonic energy, the metal ion entering graphite oxide interlayer is reduced into nanometer gold
Belong to and alloying pellet, still aging metal and the alloy crystal growth increase crystal particle diameter of allowing, and make it be distributed all
Even.While reduced nano metal and alloy, remove the oxy radical on graphite oxide surface.The stream of the present invention
Amount unit L/min represents the gas flow in unit volume, with adapt to dissimilar and model container or
Stove.
Four, pyrolysis, with distilled water by mixed reaction solution washing to pH value 6.5～7.5, filters, after filtration
The solid matter obtained is placed in high-temperature atmosphere furnace, is 0.4～1.2m at flow3Under the protective gas protection of/h,
Being warming up to 180～500 DEG C with the heating rate of 3～10 DEG C/h, low temperature pyrogenation processes 3～8h, is naturally cooling to room temperature,
Obtain the graphite composite material after nano metal and alloy and reduction.
Protective gas is more than one of nitrogen, argon and helium.
Step 4 low temperature pyrogenation processes, and eliminates oxygen-containing functional group, reduces graphite oxide, makes this also simultaneously
The residual impurity produced in former course of reaction is evaporated.
Five, the graphite composite wood after cladding, preparation mass fraction 10～the nano metal of 30% and alloy and reduction
Material aqueous solution, adding quality is nano metal and alloy and graphite composite material 4～the covering of 14%, carries out
Liquid-phase mixing, rotating speed is 200～1000r/min, mechanical agitation 40～100min, then uses the spraying of prior art
Drying machine atomization pelletize, obtains natural graphite cathode composite material precursor.
Covering is more than one of Colophonium, Polyethylene Glycol and phenolic resin.
The liquid-phase mixing of step 5 can make covering be evenly coated at outside graphite, obtains class through mist projection granulating spherical
Presoma, beneficially high temperature solid-state diffusion reaction.
Six, sintering, puts into tablet machine by natural graphite cathode composite material precursor and is pressed into diameter 300mm
The blank of × highly 200mm, pressure is 3～10MPa, and the pressed compact time is 0.5～3.0 hour, at gas stream
Amount is 0.4～1.2m3Under the protective gas atmosphere of/h, it is warming up to the heating rate of 60-120 DEG C/h
700～1200 DEG C, sinter 8～13h, naturally cool to room temperature, pulverize, obtain natural graphite cathode composite.
Protective gas is more than one of nitrogen, argon and helium.
Step 6 is pressed into blank, makes matrix combine closely with coating, and during sintering, covering occurs
Thermal decomposition, generates uniform amorphous carbon and is coated on graphite surface, the natural graphite cathode composite obtained
Tap density is big.
The natural graphite cathode composite that the inventive method prepares, the interlayer at graphite matrix is distributed
The metal of nanoscale scope and the granule of alloy, form interlayer " bridging connects ", nano metal and alloy mass
For the 0.05～5% of graphite quality, graphite matrix is coated with carbon coating layer, and the predecessor quality of carbon coating layer is
The 4～14% of the quality sum of nano metal and alloy and graphite, the predecessor of carbon coating layer be covering Colophonium,
Polyethylene Glycol and the one of phenolic resin and more than, graphite is the native graphite of quality phosphorus content more than 99%.
Although the polarity oxy radical of graphite oxide can increase its dissolubility in aqueous solution, for embedding stone
Between layer of ink, reducing metal ions reaction creates advantage, but which reduces the electrical conductivity of graphite material, institute
To need to remove the oxy radical on graphite oxide surface.In the method for the present invention, mainly utilize metal ion
The oxygen-containing group such as carboxyl and the ether on graphite oxide surface are removed in excessive reductant reduction during reduction reaction
Group, nubbin is removed further by the pyrolysis processing of step 4.Utilize the preparation oxidation of step one electrolytic oxidation
Graphite can reduce preparation cost, reduces environmental pollution.
The natural graphite cathode composite that the method for the present invention prepares, uses Jeol Ltd.
The nano metal of the JEM-2100F type transmission electron microscopy observation native graphite interlayer of JEOL and alloy, use
The Mastersizer 3000E type laser particle size analyzer of Malvern Instr Ltd. of Britain records particle mean size,
Vibration density is recorded with the DISSO-LEAD TAP-2S tap density tester of Lu Gen Instrument Ltd. of the U.S.
Degree, tests powder-compacting with the CARVER4350 type compacted density instrument of Mai Kenuo Technology Co., Ltd. of the U.S. close
Degree, records specific surface area with the NOVA 4000E specific-surface area detection instrument of Kang Ta instrument company of the U.S..
Make negative pole with the natural graphite cathode composite of embodiment, carry out half-cell test, native graphite
Anode material, conductive agent white carbon black SP, binding agent PVdF are according to mass ratio 92:3:5, with N-methyl pyrrole
Pyrrolidone NMP is applied on Copper Foil after making solvent mix homogeneously, after 110 DEG C are dried 10 hours, and spreading punching,
It is to electrode by metal lithium sheet, uses 1mol L-1LiPF6/DMC+DEC+EC (volume ratio is 1:1:1) is electrolysed
Liquid, in the German Braun MBRAUN glove box of high-purity argon gas protection, makes the experiment of CR2032 button
Battery.With the CT2001A type Bluepoint battery test system of Lan electricity electronics limited company of Wuhan City, record
1C discharge capacity mAh/g first, efficiency % first, utilize the 100th week 1C of natural graphite cathode composite
Discharge capacity is calculated 100 weeks circulation volume conservation rate % with the ratio of the 1st week 1C discharge capacity.Use Shanghai
The XTH-1S-C type standard thermostatic constant moisture test case of Xian Zhi Electronic Science and Technology Co., Ltd., in conjunction with Wuhan City's indigo plant electricity
The CT2001A type Bluepoint battery test system test natural graphite cathode composite of electronics limited company
High/low temperature charge/discharge capacity, utilize-25 DEG C of the 1st week 0.2C discharge capacities of natural graphite cathode composite with
The ratio of 25 DEG C of the 1st week 0.2C discharge capacities is calculated-25 DEG C of capability retention %.
Embodiment 1
One, weighing 500g carbon content 99%, particle diameter D50 is the native graphite of 8.0 μm, 1750g mass
The formic acid solution electrolyte of number 60%, the electric current density between anode and negative electrode is 10mA/cm2, it is electrolysed oxygen
Change native graphite 4.0h, make graphite layers away from increasing to 0.4～0.7nm, with distilled water wash pH value to 6.5,
Filtering, 60 DEG C of drying obtain graphite oxide.
Two, graphite oxide is configured to the graphite oxide aqueous solution of mass content 30%, adds metal ion
Molar concentration be the tin acetate of 0.1mol/L and cobalt acetate can intercalation hybrid metal solion, addition is oxygen
3 times of graphite aqueous solution volume, frequency is 5.0KHz, and power density is 0.30w/cm2, ultrasonic disperse
60min, obtains graphite oxide metallic ion mixed liquor.
Three, nitrogen flow is 0.15L/min, and controlling ultrasonic response still temperature is 45 DEG C, in supersonic frequency
2.5KHz, power density 0.25w/cm2Under the conditions of, it is slowly added to mass content 10% hydrazine hydrate solution to super
In the graphite oxide metallic ion mixed liquor of sound wave reactor, hydrazine hydrate with the mol ratio of metal ion is
2.05:1.Hydrazine hydrate solution continues ultrasonic disperse 120min after adding, and drips ammonia during reduction reaction
Water makes solution ph be maintained at 8.0, the still aging 2h of mixed reaction solution after ultrasonic disperse.
Four, after being aged with distilled water, mixed reaction solution pH value washs to 6.5, filters, obtains after filtration
Solid matter be placed in high-temperature atmosphere furnace, at nitrogen flow 0.4m3Under the protective gas protection of/h, with 3 DEG C
The heating rate of/h is warming up to 180 DEG C, and low temperature pyrogenation processes 8h, is naturally cooling to room temperature, obtains nanometer gold
Belong to and alloy with reduction after graphite composite material.
Five, the graphite composite material aqueous solution after the preparation nano metal of mass fraction 10% and alloy and reduction,
Add the Colophonium that mass fraction is nano metal and alloy and graphite composite material 4%, speed of agitator 200r/min,
Mechanical agitation 40min, utilizes spray dryer to be atomized pelletize, obtains natural graphite cathode composite material precursor.
Six, by natural graphite cathode composite material precursor under pressure 3Mpa, pressed compact 3.0h, it is pressed into straight
The blank of footpath 300mm × highly 200mm, is 0.4m at nitrogen flow3Under the protective gas atmosphere of/h,
It is warming up to 700 DEG C with the heating rate of 60 DEG C/h, sinters 13h, naturally cool to room temperature, pulverize, obtain sky
So graphite cathode composite.
After the natural graphite cathode composite that embodiment 1 prepares is crossed 200 mesh sieves, do physical property and change
Learn performance test.Through surveying, granularity D50=10.16 μm, specific surface area is 5.78m2/ g, tap density is
1.12g/cm3, powder body compacted density is 1.86g/cm3.The 1C of natural graphite cathode composite discharges first
Capacity is 367.4mAh/g, and efficiency is 91.5% first, circulation >=96.2% in 100 weeks, and-25 DEG C, 0.2C holds
Amount conservation rate 80.5%, is shown in Table 1.
Embodiment 2
One, weighing 500g carbon content 99%, particle diameter D50 is the native graphite of 11.0 μm, 1900g mass
The acetic acid solution electrolyte of number 56%, the electric current density between anode and negative electrode is 15mA/cm2, it is electrolysed oxygen
Change native graphite 3.5h, make graphite layers away from increasing to 0.4～0.7nm, with distilled water wash p H-number to 6.5,
Filtering, 60 DEG C of drying obtain graphite oxide.
Two, graphite oxide is configured to the graphite oxide aqueous solution of mass content 38%, adds metal ion
Molar concentration be the tin acetate of 0.28mol/L and nickel acetate can intercalation hybrid metal solion, addition is
3 times of graphite oxide aqueous solution volume, frequency is 4.2KHz, power density 0.30w/cm2, ultrasonic disperse
53min, obtains graphite oxide metallic ion mixed liquor.
Three, nitrogen flow is 0.15L/min, and controlling ultrasonic response still temperature is 53 DEG C, in supersonic frequency
2.1KHz, power density 0.25w/cm2Under the conditions of, it is slowly added to mass content 13% hydrazine hydrate solution to super
In the graphite oxide metallic ion mixed liquor of sound wave reactor, hydrazine hydrate with the mol ratio of metal ion is
2.21:1.Hydrazine hydrate solution continues ultrasonic disperse 104min after adding, and drips ammonia during reduction reaction
Water makes solution ph be maintained at 8.0, the still aging 3.2h of mixed reaction solution after ultrasonic disperse.
Four, after being aged with distilled water, mixed reaction solution pH value washs to 6.5, filters, obtains after filtration
Solid matter be placed in high-temperature atmosphere furnace, at nitrogen flow 0.4m3Under the protective gas protection of/h, with 3 DEG C
The heating rate of/h is warming up to 180 DEG C, and low temperature pyrogenation processes 8h, is naturally cooling to room temperature, obtains nanometer gold
Belong to and alloy with reduction after graphite composite material.
Five, the preparation nano metal of mass fraction 14% and alloy and graphite composite material aqueous solution, add matter
Amount number is the Colophonium of nano metal and alloy and graphite composite material 6%, speed of agitator 200r/min, machinery
Stirring 52min, utilizes spray dryer to be atomized pelletize, obtains natural graphite cathode composite material precursor.
Six, by natural graphite cathode composite material precursor under pressure 3Mpa, pressed compact 3.0h, it is pressed into straight
The blank of footpath 300mm × highly 200mm, is 0.4m at nitrogen flow3Under the protective gas atmosphere of/h,
It is warming up to 800 DEG C with the heating rate of 60 DEG C/h, sinters 12h, naturally cool to room temperature, pulverize, obtain sky
So graphite cathode composite.
After the natural graphite cathode composite that embodiment 2 prepares is crossed 200 mesh sieves, do physical property and change
Learn performance test.Through surveying, granularity D50=13.12 μm, specific surface area is 4.85m2/ g, tap density is
1.14g/cm3, powder body compacted density is 1.82g/cm3.The 1C of natural graphite cathode composite discharges first
Capacity is 362.3mAh/g, and efficiency is 90.5% first, circulation >=95.7% in 100 weeks, and-25 DEG C, 0.2C holds
Amount conservation rate 81.3%, is shown in Table 1.
Embodiment 3
One, weighing 500g carbon content 99%, particle diameter D50 is the native graphite of 14.0 μm, 2050g mass
The phosphoric acid solution electrolyte of number 50%, the electric current density between anode and negative electrode is 20mA/cm2, it is electrolysed oxygen
Change native graphite 3.0h, make graphite layers away from increasing to 0.4～0.7nm, with distilled water wash pH value to 6.5,
Filtering, 60 DEG C of drying obtain graphite oxide.
Two, graphite oxide is configured to the graphite oxide aqueous solution of mass content 46%, adds metal ion
Molar concentration be the STANNOUS SULPHATE CRYSTALLINE of 0.46mol/L and manganese sulfate can intercalation hybrid metal solion, addition is
3 times of graphite oxide aqueous solution volume, frequency is 3.4KHz, power density 0.37w/cm2, ultrasonic disperse
46min, obtains graphite oxide metallic ion mixed liquor.
Three, argon flow amount is 0.30L/min, and controlling ultrasonic response still temperature is 61 DEG C, in supersonic frequency
1.7KHz, power density 0.30w/cm2Under the conditions of, it is slowly added to mass content 16% hydroxylamine solution to ultrasonic
In the graphite oxide metallic ion mixed liquor of ripple reactor, azanol is 2.37:1 with the mol ratio of metal ion.
Hydroxylamine solution continues ultrasonic disperse 88min after adding, and drips ammonia and make pH value of solution during reduction reaction
Value is maintained at 8.5, the still aging 4.4h of mixed reaction solution after ultrasonic disperse.
Four, after being aged with distilled water, mixed reaction solution pH value washs to 7.0, filters, obtains after filtration
Solid matter be placed in high-temperature atmosphere furnace, at argon flow amount 0.8m3Under the protective gas protection of/h, with 6 DEG C
The heating rate of/h is warming up to 340 DEG C, and low temperature pyrogenation processes 5h, is naturally cooling to room temperature, obtains nanometer gold
Belong to and alloy with reduction after graphite composite material.
Five, the preparation nano metal of mass fraction 18% and alloy and graphite composite material aqueous solution, add matter
Amount number is the Polyethylene Glycol of nano metal and alloy and graphite composite material 8%, speed of agitator 600r/min,
Mechanical agitation 64min, utilizes spray dryer to be atomized pelletize, obtains natural graphite cathode composite material precursor.
Six, by natural graphite cathode composite material precursor under pressure 6Mpa, pressed compact 1.75h, it is pressed into
The blank of diameter 300mm × highly 200mm, is 0.8m at argon flow amount3Under the protective gas atmosphere of/h,
It is warming up to 900 DEG C with the heating rate of 90 DEG C/h, sinters 11h, naturally cool to room temperature, pulverize, obtain sky
So graphite cathode composite.
After the natural graphite cathode composite that embodiment 3 prepares is crossed 200 mesh sieves, do physical property and change
Learn performance test.Through surveying, granularity D50=16.43 μm, specific surface area is 4.04m2/ g, tap density is
1.23g/cm3, powder body compacted density is 1.92g/cm3.The 1C of natural graphite cathode composite discharges first
Capacity is 360.5mAh/g, and efficiency is 91.7% first, circulation >=95.0% in 100 weeks, and-25 DEG C, 0.2C holds
Amount conservation rate 83.0%, is shown in Table 1.As in figure 2 it is shown, native graphite is through electrolytic oxidation, metal ion intercalation,
After pyrolysis reduction, remain in that the layer structure of high-sequential, graphite layers away from for about 0.3407nm,
There is slight expansion away from 0.3354nm in more satisfactory graphite layers；Meanwhile, Sn2+Radius is 0.093nm, Mn2+
Radius is 0.091nm, under ultrasonication, it can be ensured that be inserted into the graphite oxide that interlamellar spacing is 0.4～07nm
Interlayer；Fig. 3, it is shown that the metal of graphite layers generation and alloying pellet are in natural graphite flakes
A length of about the 0.3409nm of particle diameter of layer axial direction, close to modified graphite layers away from 0.3407nm,
Show that graphite layers forms nano metal and " bridging connects " of alloy.In table 1, compare comparative example, embodiment
The powder body compacted density of 3 materials can be the most interlayer modified 1.63g/cm3It is promoted to 1.92g/cm3, show nanometer
The density of metal and alloy is relatively big, is effectively improved the powder body compacted density of composite.
Embodiment 4
One, weighing 500g carbon content 99%, particle diameter D50 is the native graphite of 17.0 μm, 2200g mass
The phosphoric acid solution electrolyte of number 43%, the electric current density between anode and negative electrode is 25mA/cm2, it is electrolysed oxygen
Change native graphite 2.5h, make graphite layers away from increasing to 0.4～0.7nm, with distilled water wash pH value to 7.0,
Filtering, 60 DEG C of drying obtain graphite oxide.
Two, graphite oxide is configured to the graphite oxide aqueous solution of mass content 54%, adds metal ion
Molar concentration be the nickel sulfate of 0.64mol/L and cobaltous sulfate can intercalation hybrid metal solion, addition is
3 times of graphite oxide aqueous solution volume, frequency is 2.6KHz, power density 0.37w/cm2, ultrasonic disperse
39min, obtains graphite oxide metallic ion mixed liquor.
Three, under argon flow amount is 0.30L/min, controlling ultrasonic response still temperature is 69 DEG C, at supersonic frequency
Rate 1.3KHz, power density 0.30w/cm2Under the conditions of, it is slowly added to mass content 19% hydroxylamine solution to super
In the graphite oxide metallic ion mixed liquor of sound wave reactor, azanol is 2.53 with the mol ratio of metal ion:
1.Hydroxylamine solution continues ultrasonic disperse 72min after adding, and drips ammonia and make solution during reduction reaction
PH value is maintained at 8.5, solution left standstill ageing 5.6h after ultrasonic disperse.
Four, after being aged with distilled water, mixed reaction solution pH value washs to 7.0, filters, obtains after filtration
Solid matter be placed in high-temperature atmosphere furnace, at argon flow amount 0.8m3Under the protective gas protection of/h, with 6 DEG C
The heating rate of/h is warming up to 340 DEG C, and isothermal pyrolysis processes 5h, is naturally cooling to room temperature, obtains nanometer gold
Belong to and alloy with reduction after graphite composite material.
Five, the preparation nano metal of mass fraction 22% and alloy and graphite composite material aqueous solution, add matter
Amount number is the Polyethylene Glycol of nano metal and alloy and graphite composite material 10%, speed of agitator 600r/min,
Mechanical agitation 76min, utilizes spray dryer to be atomized pelletize, obtains natural graphite cathode composite material precursor.
Six, by natural graphite cathode composite material precursor under pressure 6Mpa, pressed compact 1.75h, it is pressed into
The blank of diameter 300mm × highly 200mm, is 0.8m at argon flow amount3Under the protective gas atmosphere of/h,
It is warming up to 1000 DEG C with the heating rate of 90 DEG C/h, sinters 10h, naturally cool to room temperature, pulverize, obtain
Natural graphite cathode composite.
After the natural graphite cathode composite that embodiment 4 prepares is crossed 200 mesh sieves, do physical property and change
Learn performance test.Through surveying, granularity D50=19.27m, specific surface area is 3.17m2/ g, tap density is
1.19g/cm3, powder body compacted density is 1.94g/cm3.The 1C of natural graphite cathode composite discharges first
Capacity is 362.5mAh/g, and efficiency is 92.0% first, circulation >=95.3% in 100 weeks, and-25 DEG C, 0.2C holds
Amount conservation rate 80.1%, is shown in Table 1.
Embodiment 5
One, weighing 500g carbon content 99%, particle diameter D50 is the native graphite of 20.0 μm, 2350g mass
The salpeter solution electrolyte of number 37%, the electric current density between anode and negative electrode is 30mA/cm2, it is electrolysed oxygen
Change native graphite 2.0h, make graphite layers away from increasing to 0.4～0.7nm, with distilled water wash pH value to 7.0,
Filtering, 60 DEG C of drying obtain graphite oxide.
Two, graphite oxide is configured to the graphite oxide aqueous solution of mass content 62%, adds metal ion
Molar concentration be the manganese nitrate of 0.82mol/L and cobalt nitrate can intercalation hybrid metal solion, addition is
3 times of graphite oxide aqueous solution volume, frequency is 1.8KHz, power density 0.45w/cm2, ultrasonic disperse
32min, obtains graphite oxide metallic ion mixed liquor.
Three, helium gas flow is 0.45L/min, and controlling ultrasonic response still temperature is 77 DEG C, in supersonic frequency
0.9KHz, power density 0.35w/cm2Under the conditions of, it is slowly added to mass content 22% sodium borohydride solution extremely
In the graphite oxide metallic ion mixed liquor of ultrasonic response still, sodium borohydride and the mol ratio of metal ion
For 2.69:1.Sodium borohydride solution continues ultrasonic disperse 56min after adding, and drips during reduction reaction
Adding ammonia makes solution ph be maintained at 9.0, the still aging 6.8h of mixed reaction solution after ultrasonic disperse.
Four, after being aged with distilled water, mixed reaction solution pH value washs to 7.5, filters, obtains after filtration
Solid matter be placed in high-temperature atmosphere furnace, at helium gas flow 1.2m3Under the protective gas protection of/h, with 10 DEG C
The heating rate of/h is warming up to 500 DEG C, and low temperature pyrogenation processes 3h, is naturally cooling to room temperature, obtains nanometer gold
Belong to and alloy with reduction after graphite composite material.
Five, the preparation nano metal of mass fraction 26% and alloy and graphite composite material aqueous solution, add matter
Amount number is the phenolic resin of nano metal and alloy and graphite composite material 12%, speed of agitator 1000r/min,
Mechanical agitation 88min, utilizes spray dryer to be atomized pelletize, obtains natural graphite cathode composite material precursor.
Six, by natural graphite cathode composite material precursor under pressure 10Mpa, pressed compact 0.5h, it is pressed into
The blank of diameter 300mm × highly 200mm, is 1.2m at helium gas flow3Under the protective gas atmosphere of/h,
It is warming up to 1100 DEG C with the heating rate of 120 DEG C/h, sinters 9h, naturally cool to room temperature, pulverize, obtain
Natural graphite cathode composite.
After the natural graphite cathode composite that embodiment 5 prepares is crossed 200 mesh sieves, do physical property and change
Learn performance test.Through surveying, granularity D50=22.97 μm, specific surface area is 3.04m2/ g, tap density is
1.27g/cm3, powder body compacted density is 1.96g/cm3.The 1C of natural graphite cathode composite discharges first
Capacity is 359.4mAh/g, and efficiency is 90.3% first, circulation >=94.9% in 100 weeks, and-25 DEG C, 0.2C holds
Amount conservation rate 82.5%, is shown in Table 1.
Embodiment 6
One, weighing 500g carbon content 99%, particle diameter D50 is the native graphite of 23.0 μm, 2500g mass
The salpeter solution electrolyte of number 30%, the electric current density between anode and negative electrode is 35mA/cm2, it is electrolysed oxygen
Change native graphite 1.5h, make graphite layers away from increasing to 0.4～0.7nm, with distilled water wash pH value to 7.0,
Filtering, 60 DEG C of drying obtain graphite oxide.
Two, graphite oxide is configured to the graphite oxide aqueous solution of mass content 70%, adds metal ion
Molar concentration be the nickel nitrate of 1.0mol/L and manganese nitrate can intercalation hybrid metal solion, addition is oxygen
3 times of graphite aqueous solution volume, frequency is 1.0KHz, and power density is 0.45w/cm2, ultrasonic disperse
25min, obtains graphite oxide metallic ion mixed liquor.
Three, helium gas flow is 0.45L/min, and controlling ultrasonic response still temperature is 85 DEG C, in supersonic frequency
0.5KHz, power density 0.35w/cm2Under the conditions of, it is slowly added to mass content 25% sodium borohydride solution and surpasses
In the graphite oxide metallic ion mixed liquor of sound wave reactor, sodium borohydride with the mol ratio of metal ion is
2.85:1.Sodium borohydride solution continues ultrasonic disperse 40min after adding, and drips during reduction reaction
Ammonia makes solution ph be maintained at 9.0, the still aging 8h of mixed reaction solution after ultrasonic disperse.
Four, after being aged with distilled water, mixed reaction solution pH value washs to 7.5, filters, obtains after filtration
Solid matter be placed in high-temperature atmosphere furnace, at helium gas flow 1.2m3Under the protective gas protection of/h, with 10 DEG C
The heating rate of/h is warming up to 500 DEG C, and low temperature pyrogenation processes 3h, is naturally cooling to room temperature, obtains nanometer gold
Belong to and alloy with reduction after graphite composite material.
Five, the preparation nano metal of mass fraction 30% and alloy and graphite composite material aqueous solution, add matter
Amount number is the phenolic resin of nano metal and alloy and graphite composite material 14%, speed of agitator 1000r/min,
Mechanical agitation 100min, utilizes spray dryer to be atomized pelletize, obtains natural graphite cathode composite forerunner
Body.
Six, by natural graphite cathode composite material precursor under pressure 10Mpa, pressed compact 0.5h, it is pressed into
The blank of diameter 300mm × highly 200mm, is 1.2m at helium gas flow3Under the protective gas atmosphere of/h,
It is warming up to 1200 DEG C with the heating rate of 120 DEG C/h, sinters 8h, naturally cool to room temperature, pulverize, obtain
Natural graphite cathode composite.
After the natural graphite cathode composite that embodiment 6 prepares is crossed 200 mesh sieves, do physical property and change
Learn performance test.Through surveying, granularity D50=25.83 μm, specific surface area is 2.55m2/ g, tap density is
1.24g/cm3, powder body compacted density is 1.90g/cm3.The 1C of natural graphite cathode composite discharges first
Capacity is 355.3mAh/g, and efficiency is 89.9% first, circulation >=95.5% in 100 weeks, and-25 DEG C, 0.2C holds
Amount conservation rate 83.4%, is shown in Table 1.
Comparative example
Weighing 500g carbon content 99%, particle diameter D50 is the native graphite of 16.0 μm, is configured to mass content
The native graphite aqueous solution of 20%, adds the coated with polyethylene glycol agent that mass content is native graphite 8%, stirring
Rotating speed 600r/min, mechanical agitation 70min, utilize spray dryer to be atomized pelletize, obtain modified natural graphite
Negative material presoma.Modified natural graphite negative material presoma is carried out pressed compact, under pressure 6Mpa,
Pressed compact 1.75h, is pressed into the blank of diameter 300mm × highly 200mm, is 1.2m at nitrogen flow3/h
Protective gas atmosphere under, be warming up to 1200 DEG C with the heating rate of 120 DEG C/h, sinter 8h, the coldest
But to room temperature, pulverize, obtain modified natural graphite negative material.
After the natural graphite cathode composite that comparative example prepares is crossed 200 mesh sieves, do physical property and chemistry
Performance test.Through surveying, granularity D50=18.43 μm, specific surface area are 3.48m2/ g, tap density is
0.95g/cm3, powder body compacted density is 1.63g/cm3.The 1C of material discharge capacity first is 337.5mAh/g,
Efficiency is 84.1% first, circulation >=88.0% in 100 weeks ,-25 DEG C, 0.2C capability retention 67.3%.
In the present invention, intercalation metal ion stannum, cobalt, nickel and manganese are provided by same acid group slaine, metal from
Sub-radius size and chemical property are close, reducible generation binary or ternary alloy three-partalloy, alloy in solution system
There is superior cycle performance, higher specific capacity and multiplying power property.Described protective gas be nitrogen,
Argon and helium, gas chemistry is stable, but one or more are used in mixed way.Described covering Colophonium,
Polyethylene Glycol and phenolic resin are organic coating agent, and native graphite can realize monolayer or many in any order
Layer cladding.
The present invention is distributed the metal of nanoscale scope and the granule of alloy at the interlayer of graphite matrix, is formed
Interlayer " bridging connects ", the granule of nano metal and alloy has good electric conductivity, metal and alloy and has storage
Lithium ability, effectively promotes native graphite capacity and graphite layers conductivity, and graphite matrix is coated with carbon cladding
Layer, in suppression natural graphite negative electrode material charge and discharge process, graphite linings is stripped, and promotes natural graphite cathode material
The cycle performance of material.
The method of the present invention uses electrochemical oxidation process to prepare graphite oxide, decreases Strong oxdiative acid, Strong oxdiative
The use of agent, reduces the pollution to environment, can effectively control stone by controlling electric current density and electrolytic oxidation time
Ink sheet interlamellar spacing, makes to be prone to embed between graphite flake layer by intercalation metal ion, reduces graphite flake layer and peel off.
By at native graphite Intercalation reaction metal ion, reduction generates nano metal and alloy, effectively increases sky
So graphite c-axis direction electronic conductivity, improves the big multiplying power discharging property of natural graphite negative electrode material and low
Warm nature energy, metal alloy has storage lithium ability the most by force, also improves the electric discharge specific volume of natural graphite negative electrode material
Amount.Graphite composite material after nano metal and alloy and reduction is coated with, improves electrolyte to stone
Ink layer corrosion, it is therefore prevented that graphite flake layer comes off, and improves the cycle performance of natural graphite negative electrode material.
Table 1 embodiment and the physical property of comparative example and electrochemical property test result
Claims (10)
1. a natural graphite negative electrode material method of modifying, comprises the following steps:
One, electrolytic oxidation, by native graphite and electrolyte 1.0:3.5 in mass ratio～5.0, puts after mixed pulp
Entering electrolysis bath, the electric current density controlled between anode and negative electrode is 10～35mA/cm2, the electrolytic oxidation time is
1.5～4.0h, make the interlamellar spacing of native graphite increase to 0.4～0.7nm, washing make its pH value to 6.5～7.0,
Filter, directly 60 DEG C of drying, obtain graphite oxide；
Two, insert metal ion, graphite oxide be configured to mass content 30～the graphite oxide aqueous solution of 70%,
Add metal ion molar concentration be 0.1～1.0mol/L can intercalation hybrid metal solion, aoxidize stone
Ink solution with can intercalation hybrid metal solion volume ratio be 3:1, be 1～5KHz in frequency, power is close
Degree is 0.30～0.45w/cm2Under conditions of, ultrasonic disperse 25～60min, obtain graphite oxide metal ion and mix
Close solution；Described can intercalation hybrid metal solion be the two or three of stannum, cobalt, nickel and manganese salt solution,
The molar concentration rate of two metal ion species is 1:1, and the molar concentration rate of three metal ion species is 1:1:1；
Three, reduction, controlling temperature is 45～85 DEG C, in supersonic frequency 0.5～2.5KHz, power density
0.25～0.35w/cm2Under the conditions of, add mass content 10～25% reductant solution to graphite oxide metal from
In sub-mixed solution, reducing agent is 2.05 with the mol ratio of metal ion in graphite oxide metallic ion mixed liquor
～2.85:1, reductant solution adds complete, continues ultrasonic disperse 40～120min, during reduction reaction
Making solution ph be maintained at 8.0～9.0, the mixed reaction solution after ultrasonic disperse terminates at room temperature stands old
Change 2～8h；Described reducing agent is the one in hydrazine hydrate, azanol or sodium borohydride；
Four, pyrolysis, by mixed reaction solution washing to pH value 6.5～7.5, filters, and obtain after filtration consolidates
Body material is placed in high-temperature atmosphere furnace, is warming up to 180～500 DEG C with the heating rate of 3～10 DEG C/h, low temperature pyrogenation
Process 3～8h, be naturally cooling to room temperature, obtain the graphite composite material after nano metal and alloy and reduction；
Five, the graphite composite wood after cladding, preparation mass fraction 10～the nano metal of 30% and alloy and reduction
Material aqueous solution, adding quality is nano metal and alloy and graphite composite material 4～the covering of 14%, carries out
Liquid-phase mixing, rotating speed is 200～1000r/min, mechanical agitation 40～100min, is atomized pelletize, obtains natural stone
Ink anode material presoma；Described covering is more than one of Colophonium, Polyethylene Glycol and phenolic resin；
Six, sintering, heats up natural graphite cathode composite material precursor with the heating rate of 60-120 DEG C/h
To 700～1200 DEG C, sinter 8～13h, naturally cool to room temperature, obtain natural graphite cathode composite.
Natural graphite negative electrode material method of modifying the most according to claim 1, it is characterised in that: described
The quality phosphorus content of the native graphite of step one is more than 99%, and granularity D50 is 8～23 μm.
Natural graphite negative electrode material method of modifying the most according to claim 1, it is characterised in that: described
The electrolyte of step one is the one in mass content 30～the phosphoric acid of 60%, nitric acid, formic acid or acetic acid.
Natural graphite negative electrode material method of modifying the most according to claim 1, it is characterised in that: described
Two or three metal ion of step 2 is same acid group.
Natural graphite negative electrode material method of modifying the most according to claim 1, it is characterised in that: described
The pink salt of step 2 is the one in tin acetate, STANNOUS SULPHATE CRYSTALLINE and nitric acid stannum；Cobalt salt be cobalt acetate, cobaltous sulfate and
One in cobalt nitrate；Nickel salt is the one in nickel acetate, nickel sulfate and nickel nitrate；Manganese salt be manganese acetate,
One in manganese sulfate and manganese nitrate.
Natural graphite negative electrode material method of modifying the most according to claim 1, it is characterised in that: described
Step 3 reduction is carried out under the protective gas atmosphere that flow is 0.15～0.45L/min；Described step 4 heat
Solution is 0.4～1.2m at flow3Carry out under the protective gas protection of/h；Described step 6 is sintered in gas flow
It is 0.4～1.2m3Carry out under the protective gas atmosphere of/h；Protective gas is the one of nitrogen, argon and helium
More than Zhong.
Natural graphite negative electrode material method of modifying the most according to claim 1, it is characterised in that: described
Dripping ammonia in the former course of reaction of step 3 makes solution ph be maintained at 8.0～9.0.
Natural graphite negative electrode material method of modifying the most according to claim 1, it is characterised in that: described
Natural graphite cathode composite material precursor is put into tablet machine and is pressed into diameter 300mm × highly by step 6
The blank of 200mm, pressure is 3～10MPa, and the pressed compact time is 0.5～3.0 hour.
Natural graphite negative electrode material method of modifying the most according to claim 1, it is characterised in that: described
Pulverize after step 6 sintering.
10. a natural graphite cathode composite, graphite matrix is coated with carbon coating layer, it is characterised in that:
The interlayer of described graphite matrix is distributed metal and the alloy of nanoscale scope, nano metal and alloy mass
For graphite quality 0.05～5%；The predecessor quality of described carbon coating layer is nano metal and alloy and graphite
The 4～14% of quality sum；The predecessor of carbon coating layer is covering Colophonium, Polyethylene Glycol and phenolic resin
More than one；Described graphite is the native graphite of quality phosphorus content more than 99%.
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| CN107017397A (en) * | 2017-06-01 | 2017-08-04 | 湖北工程学院 | Graphite composite material and application thereof, preparation method and lithium ion battery |
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| CN112038631A (en) * | 2020-09-03 | 2020-12-04 | 青海凯金新能源材料有限公司 | Lithium battery electrode plate with surface coated with natural graphite and processing technology thereof |
| CN114335462B (en) * | 2021-12-24 | 2023-06-02 | 陕西煤业化工技术研究院有限责任公司 | Graphite negative electrode material for low temperature, preparation method thereof and lithium battery |
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