CN108123111A - A kind of lithium ion battery silicon substrate composite negative pole material, its preparation method and the negative electrode of lithium ion battery comprising the material - Google Patents
A kind of lithium ion battery silicon substrate composite negative pole material, its preparation method and the negative electrode of lithium ion battery comprising the material Download PDFInfo
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- CN108123111A CN108123111A CN201611071114.0A CN201611071114A CN108123111A CN 108123111 A CN108123111 A CN 108123111A CN 201611071114 A CN201611071114 A CN 201611071114A CN 108123111 A CN108123111 A CN 108123111A
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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
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- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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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
- H01M4/625—Carbon or graphite
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of lithium ion battery silicon substrate composite negative pole material, its preparation method and negative electrode of lithium ion battery comprising the material.The silicon substrate composite negative pole material is made of ultra-fine silicon particle, carbon containing electric conductor, amorphous carbon, graphite, wherein, ultra-fine silicon particle surface coats one layer of carbon containing electric conductor and is evenly distributed between the graphite surface and graphite flake layer of orientations, it is coated between the ultra-fine silicon particle of carbon containing electric conductor and graphite and is combined closely by amorphous carbon, and amorphous carbon coating layer is coated in the outermost surface of graphite/amorphous carbon/carbon containing electric conductor/silicon.Its preparation method includes the following steps：Mechanochemical reaction prepares ultra-fine silicon particle；Graphite/carbon containing electric conductor presoma/silicon compound；Prepare presoma；Presoma carbonization, broken, sieving obtain silicon substrate composite negative pole material.Negative material uniform particle sizes, structural stability and electrochemical stability is good, electro-chemical activity is high.This method simple process and low cost, suitable for large-scale production.
Description
Technical field
The present invention relates to a kind of lithium ion battery silicon substrate composite negative pole material, its preparation method and lithiums comprising the material
Ion battery cathode.
Background technology
Lithium ion battery because its with operating voltage it is high, have extended cycle life, memory-less effect, self discharge effect are small, environment
The advantages that friendly, has been widely used in mobile electronic device, scale energy-accumulating power station and electric vehicle.Currently, business
The lithium ion battery negative material of change, can not mainly using graphite negative electrodes material, but its theoretical specific capacity is only 372mAh/g
Meet the requirement of following more high-energy-density and the development of high power density lithium ion battery.Therefore, the height ratio capacity for substituting carbon is found
Negative material becomes an important developing direction.
Since with highest lithium storage content (theoretical specific capacity 4200mAh/g) and abundant resource, silicon materials are considered
It is most potential to be expected to become next-generation lithium ion battery negative material.However, since larger volume during Li insertion extraction becomes
Change the silicon material structure destruction brought and material dusting, electrode structure can be caused to destroy, silicon active component is caused to lose electrical contact.
In addition the dusting of material and huge volume change, can cause being continuously generated for SEI films, be cycled so as to cause the electrochemistry of battery
Stability is poor, hinders scale application of the silicon materials as lithium ion battery negative material.
To solve the problems, such as that silicium cathode material exists in the application, researchers mainly pass through the nanosizing means of silicon at present
The grain size of silicon is reduced, reduces the absolute volume expansion of silicon, avoids material dusting.But simple nanosizing can not solve nano-silicon
The problem of " electrochemistry sintering " in cyclic process and SEI films caused by the side reaction of aggravation are continuously generated.Therefore must adopt
The means being combined with nanosizing and Composite actually should by constructing the method for multi-component multi-layer time composite material to solve silicon
The various problems present in.
CN 105609730A disclose a kind of preparation method of silicon/carbon graphite composite negative pole material, by silica flour and carbon source
Presoma disperses, be spray-dried after calcine, obtain porous spherical silicon/carbon composite particles；It adds organic carbon source and graphite carries out
Secondary spray drying obtains silicon/carbon graphite composite material after secondary clacining.But silicon/the carbon being spray-dried for the first time is compound
In particle, the reunion of silicon will necessarily occur, and then cause silicon not high in the dispersiveness and bond strength of graphite surface, charge and discharge
The huge volume expansion of silicon/carbon structure unit can cause the rupture of amorphous carbon coating layer in journey, thus the cycling of material is steady
Qualitative poor (50 weeks circulation volume conservation rate 50-83.5%).Not high (the 60- of all coulombic efficiencies of head of composite material simultaneously
75%), which also limits its applications in current lithium ion battery large-scale production.
Traditional nanometer silicon preparation method mainly includes chemical vapour deposition technique, physical evaporation method, solwution method and laser and burns
Erosion method etc., but these methods are of high cost, low yield, and lot stability is poor.Nano-silicon large specific surface area simultaneously, surface can be high, hold
Easily reunite, thus in composite material is built, in substrate material surface bad dispersibility, interface bond strength is low, is circulated throughout
Cheng Zhonghui is removed from matrix surface, has ultimately caused that the cyclical stability of silicon based composite material is poor, and being unable to reach commercialization makes
It is required that.
The content of the invention
In view of the deficiencies of the prior art, present invention aims at provide a kind of lithium ion battery silicon substrate composite negative pole material
Material, ultra-fine silicon particle reaches nano-scale, footpath narrowly distributing, is uniformly dispersed in substrate material surface, boundary in the composite negative pole material
Face bond strength is high, and composite material exhibits go out preferable structural stability and electrochemical stability, electro-chemical activity.
Another object of the present invention is to provide a kind of preparation side of the lithium ion battery silicon substrate composite negative pole material
Method, this method preparation process is simple, at low cost, easily accomplishes scale production.
Another object of the present invention is to provide a kind of negative electrode of lithium ion battery for including the silicon substrate composite negative pole material.
To achieve the above object, the present invention uses following technical scheme：
A kind of lithium ion battery silicon substrate composite negative pole material, the silicon substrate composite negative pole material is by ultra-fine silicon particle, carbon containing
Electric conductor, amorphous carbon, graphite composition, wherein, ultra-fine silicon particle surface coats one layer of carbon containing electric conductor and is evenly distributed on and takes
Between the graphite surface and graphite flake layer of arrangement, it is coated between the ultra-fine silicon particle of carbon containing electric conductor and graphite by without fixed
Shape carbon is combined closely, and is coated with amorphous carbon cladding in the outermost surface of graphite/amorphous carbon/carbon containing electric conductor/silicon
Layer.
In the present invention, by weight percentage, in the negative material comprising silicon 1-35%, graphite 45-90% is carbon containing
Electric conductor 1%-10%, amorphous carbon 5-35%.
The ultra-fine silicon particle grain size is in 10-300nm, preferably 30-100nm, surface oxide layer SiOxThickness≤
3nm, wherein, 0 ＜ x≤2.
The graphite substrate material is native graphite, micro crystal graphite, isotropism Delanium or anisotropy artificial stone
The one or more of ink.
The carbon containing electric conductor is amorphous carbon, graphene, carbon nanotubes, low carbon content silicon-oxygen-carbon ceramic material, Gao Han
Carbon amounts silicon-oxygen-carbon ceramic material, the one or more of carborundum.
The amorphous carbon coating layer be soft carbon clad, hard carbon clad or soft carbon hard carbon compound coating layer, thickness≤2
μm。
A kind of preparation method of lithium ion battery silicon substrate composite negative pole material, including at least following steps：
(1) using silica flour as raw material, it is dispersed in decentralized medium, ball milling obtains ultra-fine silicon particle dispersion liquid；
(2) a certain amount of graphite, carbon containing electric conductor presoma are added in ultra-fine silicon particle dispersion liquid, are obtained after scattered
Uniform mixed slurry, then dry, granulation obtain presoma I composite particles；
(3) presoma I composite particles and organic carbon source presoma are subjected to hot kneading, the carbon source presoma of softening is uniform
Composite particles surface is coated on, obtains precursor II；
(4) hot-pressing processing is carried out to precursor II and obtains precursor III；
(5) precursor III is crushed, and carries out isostatic pressed and handle to obtain presoma IV；
(6) presoma IV is calcined in an inert atmosphere, then the silicon substrate composite negative pole is obtained after broken, screening
Material.
The present invention prepares the ultra-fine silicon particle of high electrochemical activity, and the hand for passing through Composite using the method for mechanochemistry
Section constructs multi-component multi-layer time silicon substrate composite negative pole material, to solve the problems, such as that silicon is existing various in practical applications.The silicon substrate
In composite negative pole material, the ultra-fine silicon particle surface of high electrochemical activity coats one layer of carbon containing electric conductor and is evenly distributed on orientation
Between the graphite surface and graphite flake layer of arrangement, combined closely by the amorphous carbon of high fill-ratio, and in graphite/amorphous
The high-tap density nucleocapsid cathode that the outermost surface of carbon/carbon containing electric conductor/silicon coats amorphous carbon coating layer and forms
Material.This structure can prevent silicon from reuniting in cyclic process, and silicon and combining closely for graphite ensure that stable electricity
Son and lithium ion transport passage；The gap between graphite particle and between silicon particle can be that the volume expansion of silicon is reserved simultaneously
Space；Amorphous carbon coating layer can not only buffer the volume expansion of silicon, also help to form stable solid liquid interface, avoid
SEI films are continuously generated.Electro-chemical activity and stabilization of the silicon based anode material in cyclic process thus can be greatlyd improve
Property.
The preparation method of the present invention the step of in (1), the decentralized medium is water, ethyl alcohol, ethylene glycol, isopropanol, acetone,
One or more of hexamethylene；
Ratio of grinding media to material (mass ratio) control is 5: 1-20: 1 in the step (1)；The rotating speed of ball mill is in the step (1)
1400-2500rpm, when Ball-milling Time is 3-16 small, temperature of charge is controlled at 25-35 DEG C；The step with centrifugal separation centrifugal force
For 6000-48000 × g；
The carbon containing electric conductor presoma described in step (2) for polyacrylic acid, polyimides, phenolic resin, epoxy resin,
Glucose, graphene oxide, graphene, carbon nanotubes, organosiloxane, polysiloxane, polysiloxane with to two
The one or more of toluene cross-linking products, silicones.
Organic carbon source presoma in the step (3) is selected from coal tar pitch and petroleum asphalt, mesophase pitch, coal tar, heat
The one or more of plastic resin.
At 100-250 DEG C, organic carbon source presoma is soft state or melting for temperature of charge control in the step (3)
State, kneading time 1-4h.
Using hot moulding or hot-rolling pressure, hot pressing temperature is controlled in organic carbon source presoma for hot pressing in the step (4)
It is more than softening point temperature.
Isostatic pressed in the step (5) is isostatic cool pressing, any one in warm isostatic pressed or hot isostatic pressing, pressure
Control is in 10-250Mpa, dwell time 3-30 minute.
It it is 600-1200 DEG C in the step (6) high temperature calcining heat, when the time is 0.5-8 small.
The inert atmosphere described in step (6) is one kind in argon gas, nitrogen, helium and argon hydrogen gaseous mixture.
Silicon substrate composite negative pole material obtained by step (6) is spherical or random polygon, and median particle diameter is 5-15 μm.
A kind of negative electrode of lithium ion battery, it includes the silicon substrate composite negative pole materials.
The advantage of the invention is that：
Compared with prior art, the present invention it provides the ultra-fine silicon particle of stable, inexpensive high activity and surpasses containing this
The preparation method of the composite negative pole material of thin silicon particle.To ultra-fine silicon particle/carbon containing electric conductor presoma/graphite mixed slurry spray
Mist drying-granulating solves dispersiveness and binding characteristic of the silicon particle on graphite matrix surface；Using kneading, hot-rolling pressure, isostatic pressed
Method, it is scattered between graphite surface and graphite flake layer to enhance ultra-fine silicon particle using the flow behavior of carbon source presoma
Property and bond strength, and then the density and bond strength of silicon carbide composite particles are improved, while be conducive on composite particles surface
Form complete carbon coating layer.Preparation method that the present invention describes is simple for process, it is at low cost, be suitable for mass producing.It prepares
The silicon substrate composite negative pole material of multi-component multi-layer time structure efficiently solve silicon existing structural stability in use
With the problems such as cyclical stability is poor, SEI films are continuously generated, and material has all reversible capacities of higher head and coulombic efficiency,
Composite material has higher tap density and preferable processing performance simultaneously.There is good structure using the battery of the material
Stability and electrochemical stability.
Description of the drawings
Fig. 1 is the process route chart of the present invention.
The ultra-fine silicon particle grain size distribution obtained after Fig. 2 liquid phase ball millings.
Fig. 3 is graphite/presoma containing carbonaceous conductive/silicon composite structure section SEM (scannings that hot-rolling pressure obtains in embodiment 1
Electron microscope) figure.
Fig. 4 is silicon substrate composite negative pole material section SEM (scanning electron microscope) figure prepared in embodiment 1.
Fig. 5 is the SEM figures of the silicon substrate composite negative pole material particle surface prepared in embodiment 1.
Fig. 6 is all charging and discharging curves of head of the silicon substrate composite negative pole material prepared in embodiment 1.
Fig. 7 is the stable circulation linearity curve of the silicon substrate composite negative pole material prepared in embodiment 1.
Fig. 8 is the SEM figures of the silicon substrate composite negative pole material prepared in comparative example 1.
Fig. 9 is the SEM figures of the silicon substrate composite negative pole material prepared in comparative example 2.
Specific embodiment
The invention will be further described by the following examples, but the present invention is not limited to following embodiments.
Embodiment 1-5 and comparative example 1-2 prepares electrode and test material chemical property, test knot using following methods
Fruit is as shown in table 1.
By silicon substrate composite negative pole material, conductive agent and binding agent by mass percentage 86: 6: 8 ratio be dissolved in solvent
In, solid content 30%.Wherein binding agent uses mass ratio (CMC, 2wt%CMC is water-soluble for 1: 3 sodium carboxymethylcellulose
Liquid)-butadiene-styrene rubber (SBR, 50wt%SBR aqueous solution) compound water-based binder.Again plus 0.8% oxalic acid as etching copper foil
Acidic materials obtain uniform sizing material after being sufficiently stirred.Coated on 10 μm of copper foils, after drying 4h at room temperature, use is a diameter of
14 millimeters of punch is washed into pole piece, in 100kg/cm-2Pressure lower sheeting, be put into 120 DEG C of vacuum drying ovens dry 8 it is small when.
Pole piece is transferred in glove box, uses metal lithium sheet as cathode, Celgard2400 membranes, 1mol/L
LiPF6/ EC+DMC+EMC (v/v/v=1: 1: 1) electrolyte, CR2016 battery cases assembling button cell.In Wuhan gold promise Land
The charge-discharge test of constant current, the cycle charge-discharge under the current density of 80mA/g, charge and discharge are carried out on CT2001A battery test systems
Electric blanking voltage is compared with Li/Li+For 0.005-2V.
Embodiment 1
It is 3 μm to take 2kg median particle diameters, silicone content is the micron silica flour more than 99%, is added in 18kg deionized waters, surpasses
It after sound disperses 30min, pours into ultra-fine ball mill cavity, adds in the sodium lignin sulfonate of 0.5wt% silica flour quality.Using diameter
Zirconia ball for 0.3mm is ball-milling medium, and ratio of grinding media to material (mass ratio) is 10: 1, when ball milling 10 is small under the rotating speed of 1800rpm,
Obtain ultra-fine silicon particle dispersion liquid.
800g glucose and 5.5kg isotropism Delaniums KS6,1000rpm are added in into ultra-fine silicon particle dispersion liquid
Under rotating speed ball milling disperse 1 it is small when after obtain uniform mixed slurry.Mixed slurry is spray-dried, it is compound to obtain graininess
Powder.Kneading machine temperature is controlled as 170 DEG C by circulating heat conduction oil, powdery intermediate product obtained by the above-mentioned spray drying of 2kg is taken to put
Enter and 1h is preheated in kneading machine；It is put into the modified coal tar pitch kneading 1h of 0.88kg molten conditions；By kneading product at 170 DEG C hot-rolling pressure
10 times, the rubber shape of about 2mm thickness is formed, powder body material is broken into after cooling；Powder body material is put into rubber package set again,
150 DEG C in warm isostatic pressing machine, isostatic pressing 10 minutes under 200MPa pressure；Then formed blocks material is put into shaft furnace
In, postcooling is to room temperature when the lower 900 DEG C of calcinings 5 of nitrogen atmosphere are small；Most the silicon of silicone content 20% is obtained after broken and screening afterwards
Base composite negative pole material.
Fig. 2 is the ultra-fine silicon particle grain size distribution obtained in embodiment 1 after liquid phase ball milling, it can be seen that through 10h ball millings
Afterwards, the median particle diameter of silicon particle is 139nm.
Fig. 3 is graphite/presoma containing carbonaceous conductive/silicon composite structure section SEM (scanning electrons after hot-rolling pressure in embodiment 1
Microscope) figure, it can be seen that under the action of pressure and molten state carbon source precursor flow, orientation arrangement has occurred in graphite.
Carbon source presoma is filled between graphite flake layer, graphite and ultra-fine silicon particle are closely joined together.
Fig. 4 is silicon substrate composite negative pole material section SEM (scanning electron microscope) figure after carbonization, it can be seen that silicon particle is equal
It is even to be distributed between graphite flake layer, and combine closely with graphite；Substantial amounts of hole is generated after the carbonization of carbon source presoma, is charge and discharge
Space has been reserved in the volume expansion of silicon in electric process.
Fig. 5 schemes for silicon substrate composite negative pole material surface SEM, it can be seen that composite particles surface forms one layer of uniform nothing
Shape carbon coating layer, reduces the specific surface area of material, contacting directly for electrolyte and silicon and graphite is avoided, so as to press down
The side reaction of electrolyte processed.
Fig. 6 and Fig. 7 is respectively all charging and discharging curves of head of the silicon substrate composite negative pole material synthesized and stable circulation linearity curve.
It can be seen that the first all reversible capacities of silicon substrate composite negative pole material are 656.2mAh/g, first week coulombic efficiency is 80.1%, is followed within 50 weeks
Ring capacity retention ratio is 92.0%.
Comparative example 1
Silicon substrate composite negative pole material is prepared according to method substantially the same manner as Example 1, difference lies in：Graphite/carbon containing is led
Without hot-rolling pressure, broken, isostatic pressing step processing after electric presoma/silicon and the hot kneading of modified coal tar pitch, directly in nitrogen
The lower 900 DEG C of carbonizations of gas atmosphere, silicon substrate composite negative pole material is obtained after cooling through broken, screening.Fig. 8 is to prepare silicon in comparative example 1
Base composite negative pole material SEM schemes, it can be seen that particle surface still has exposed position, and clad is imperfect.The thus table of material
Face area is big, and first week coulombic efficiency reduces.The step of due to no hot-rolling pressure and isostatic pressed, material tap density is relatively low.
Comparative example 2
Silicon substrate composite negative pole material is prepared according to method substantially the same manner as Example 1, difference lies in：Graphite/carbon containing is led
Electric presoma/silicon and modified coal tar pitch are after hot kneading, hot-rolling pressure, it is broken after without isostatic pressing step processing, directly
900 DEG C of carbonizations in a nitrogen atmosphere obtain silicon substrate composite negative pole material after cooling through broken, screening.As shown in Figure 9, compared to
The silicon substrate composite negative pole material of direct carbonization, amorphous carbon coating layer integrality are improved after hot kneading.The jolt ramming of material
Density improves, and specific surface area reduces, and the first all coulombic efficiencies of material and cyclical stability further improve, but after performance ratio isostatic pressed
The silicon substrate composite negative pole material performance of preparation is poor.
Embodiment 2
It is 3 μm to take 2kg median particle diameters, silicone content is the micron silica flour more than 99%, is added in 18kg ethyl alcohol, ultrasound point
It after dissipating 30min, pours into ultra-fine ball mill cavity, adds in the sodium lignin sulfonate of 0.5wt% silica flour quality.Using a diameter of
The zirconia ball of 0.3mm is ball-milling medium, and ratio of grinding media to material (mass ratio) is 14: 1, when ball milling 10 is small under the rotating speed of 1800rpm, is obtained
To ultra-fine silicon particle dispersion liquid.
50g phenolic resin and 2.86kg isotropism Delanium KS6 are added in into ultra-fine silicon particle dispersion liquid,
Uniform mixed slurry is obtained after when ball milling 1 is small under 1000rpm rotating speeds.Mixed slurry is spray-dried, obtains graininess
Composite granule.Control kneading machine temperature that the above-mentioned composite granules of 2kg is taken to be put into kneading machine and are stirred for 170 DEG C by circulating heat conduction oil
Mix preheating 1h；It is put into the modified coal tar pitch kneading 1h of 0.53kg molten conditions；By kneading product, hot-rolling is pressed 10 times at 170 DEG C, shape
Into the rubber shape of about 2mm thickness, powder body material is broken into after cooling；Powdery precursor is put into rubber package set, it is quiet in temperature etc.
150 DEG C in press, isostatic pressing 10 minutes under 200MPa pressure；Then formed blocks material is put into shaft furnace, nitrogen
Postcooling is to room temperature when the lower 900 DEG C of calcinings 5 of atmosphere are small；Most the silicon substrate Compound Negative of silicone content 30% is obtained after broken and screening afterwards
Pole material.
Embodiment 3
It is 3 μm to take 2kg median particle diameters, silicone content is the micron silica flour more than 99%, is added in 18kg ethyl alcohol, ultrasound point
It after dissipating 30min, pours into ultra-fine ball mill cavity, adds in the sodium lignin sulfonate of 0.5wt% silica flour quality.Using a diameter of
The zirconia ball of 0.3mm is ball-milling medium, and ratio of grinding media to material (mass ratio) is 14: 1, when ball milling 10 is small under the rotating speed of 1800rpm, is obtained
To ultra-fine silicon particle dispersion liquid.
50g phenolic resin and 2.86kg anisotropy Delanium SFG6 are added in into ultra-fine silicon particle dispersion liquid,
Uniform mixed slurry is obtained after when ball milling 1 is small under 1000rpm rotating speeds.Mixed slurry is spray-dried, obtains graininess
Composite granule.Control kneading machine temperature that the above-mentioned composite granules of 2kg is taken to be put into kneading machine and are stirred for 170 DEG C by circulating heat conduction oil
Mix preheating 1h；It is put into the modified coal tar pitch kneading 1h of 0.53kg molten conditions；By kneading product, hot-rolling is pressed 10 times at 170 DEG C, shape
Into the rubber shape of about 2mm thickness, powder body material is broken into after cooling；Powdery precursor is put into rubber package set, it is quiet in temperature etc.
150 DEG C in press, isostatic pressing 10 minutes under 200MPa pressure；Then formed blocks material is put into shaft furnace, nitrogen
Postcooling is to room temperature when the lower 900 DEG C of calcinings 5 of atmosphere are small；Most the silicon substrate Compound Negative of silicone content 30% is obtained after broken and screening afterwards
Pole material.
Embodiment 4
It is 3 μm to take 2kg median particle diameters, silicone content is the micron silica flour more than 99%, is added in 18kg ethyl alcohol, ultrasound point
It after dissipating 30min, pours into ultra-fine ball mill cavity, adds in the sodium lignin sulfonate of 0.5wt% silica flour quality.Using a diameter of
The zirconia ball of 0.3mm is ball-milling medium, and ratio of grinding media to material (mass ratio) is 14: 1, when ball milling 10 is small under the rotating speed of 1800rpm, is obtained
To ultra-fine silicon particle dispersion liquid.
50g phenolic resin and 2.86kg anisotropy Delanium SFG15 are added in into ultra-fine silicon particle dispersion liquid,
Uniform mixed slurry is obtained after when ball milling 1 is small under 1000rpm rotating speeds.Mixed slurry is spray-dried, obtains graininess
Composite granule.Control kneading machine temperature that the above-mentioned composite granules of 2kg is taken to be put into kneading machine and are stirred for 170 DEG C by circulating heat conduction oil
Mix preheating 1h；It is put into the modified coal tar pitch kneading 1h of 0.53kg molten conditions；By kneading product, hot-rolling is pressed 10 times at 170 DEG C, shape
Into the rubber shape of about 2mm thickness, powder body material is broken into after cooling；Powdery precursor is put into rubber package set, it is quiet in temperature etc.
150 DEG C in press, isostatic pressing 10 minutes under 200MPa pressure；Then formed blocks material is put into shaft furnace, nitrogen
Postcooling is to room temperature when the lower 900 DEG C of calcinings 5 of atmosphere are small；Most the silicon substrate Compound Negative of silicone content 30% is obtained after broken and screening afterwards
Pole material.
Embodiment 5
It is 3 μm to take 2kg median particle diameters, silicone content is the micron silica flour more than 99%, is added in 18kg deionized waters, surpasses
It after sound disperses 30min, pours into ultra-fine ball mill cavity, adds in the sodium lignin sulfonate of 0.5wt% silica flour quality.Using diameter
Zirconia ball for 0.3mm is ball-milling medium, and ratio of grinding media to material (mass ratio) is 14: 1, when ball milling 10 is small under the rotating speed of 1800rpm,
Obtain ultra-fine silicon particle dispersion liquid.
It is small that ball milling 1 under 5.5kg isotropism Delanium KS6,1000rpm rotating speeds is added in into ultra-fine silicon particle dispersion liquid
When after obtain uniform mixed slurry.Mixed slurry is spray-dried, obtains particulate powder.Pass through circulating heat conduction oil control
Kneading machine temperature processed is 170 DEG C, and the above-mentioned powdery intermediate products of 2kg is taken to be put into kneading machine and stir 1h；It is put into 1.89kg moltens
The modified coal tar pitch kneading 1h of state；By kneading product at 170 DEG C hot-rolling pressure, into the sheet of 2mm thickness, powder is broken into after cooling
Material；Powdery precursor is put into rubber package set, 150 DEG C in cold isostatic press, isostatic pressing 20 under 200MPa pressure
Minute；Then formed blocks material is put into shaft furnace, postcooling is to room temperature when the lower 900 DEG C of calcinings 5 of nitrogen atmosphere are small；Finally
The silicon substrate composite negative pole material of silicone content 30% is obtained after broken and screening.
Table 1
It can be seen from the above result that the silicon substrate composite negative pole material for preparing of the present invention shows very high electro-chemical activity and excellent
Cyclical stability.
Claims (21)
1. a kind of lithium ion battery silicon substrate composite negative pole material, which is characterized in that the silicon substrate composite negative pole material is by ultra-fine silicon
Particle, carbon containing electric conductor, amorphous carbon, graphite composition, wherein, ultra-fine silicon particle surface one layer of carbon containing electric conductor of cladding is simultaneously uniform
It is distributed between the graphite surface and graphite flake layer of orientations, is coated between the ultra-fine silicon particle of carbon containing electric conductor and graphite
It is combined closely by amorphous carbon, and is coated in the outermost surface of graphite/amorphous carbon/carbon containing electric conductor/silicon without fixed
Shape carbon coating layer.
2. lithium ion battery according to claim 1 silicon substrate composite negative pole material, which is characterized in that by weight percentage
Meter, comprising：Silicon 1-35%, graphite 45-90%, carbon containing electric conductor 1%-10%, amorphous carbon 5-35%.
3. lithium ion battery according to claim 1 silicon substrate composite negative pole material, which is characterized in that the ultra-fine silicon
Grain grain size is 10-300nm, surface oxide layer SiOxThickness≤3nm, wherein, 0 ＜ x≤2.
4. lithium ion battery according to claim 1 silicon substrate composite negative pole material, which is characterized in that the ultra-fine silicon
Grain optimization grain size is 30-100nm, surface oxide layer SiOxThickness≤3nm, wherein, 0 ＜ x≤2.
5. lithium ion battery according to claim 1 silicon substrate composite negative pole material, which is characterized in that the graphite is day
So one or more of graphite, micro crystal graphite, isotropism Delanium or anisotropic Delanium.
6. lithium ion battery according to claim 1 silicon substrate composite negative pole material, which is characterized in that described to contain carbonaceous conductive
Body is amorphous carbon, graphene, carbon nanotubes, silicon-oxygen-carbon ceramic material, the one or more of carborundum.
7. lithium ion battery according to claim 1 silicon substrate composite negative pole material, which is characterized in that the amorphous carbon
Clad is soft carbon clad, hard carbon clad or soft carbon hard carbon compound coating layer.
8. a kind of preparation method of the lithium ion battery silicon substrate composite negative pole material any one of claim 1-7,
It is characterized in that, including at least following steps：
(1) using silica flour as raw material, it is dispersed in decentralized medium, ball milling obtains ultra-fine silicon particle dispersion liquid；
(2) a certain amount of graphite, carbon containing electric conductor presoma are added in ultra-fine silicon particle dispersion liquid, are obtained after scattered uniformly
Mixed slurry, it is then dry, be granulated and obtain presoma I composite particles；
(3) presoma I composite particles and organic carbon source presoma are subjected to hot kneading, the carbon source presoma of softening is uniformly coated
On composite particles surface, precursor II is obtained；
(4) hot-pressing processing is carried out to precursor II and obtains precursor III；
(5) precursor III is crushed, and carries out isostatic pressed and handle to obtain presoma IV；
(6) presoma IV is calcined in an inert atmosphere, then the silicon substrate composite negative pole material is obtained after broken, screening
Material.
9. preparation method according to claim 8, which is characterized in that in the step (1) decentralized medium for water, ethyl alcohol,
One or more of ethylene glycol, isopropanol, acetone, hexamethylene.
10. preparation method according to claim 8, which is characterized in that the grinding that mechanical milling process uses in the step (1)
Medium is the zirconia ball of diameter 0.05-0.6mm, and ball material mass ratio is controlled 5: 1-20: 1.
11. preparation method according to claim 8, which is characterized in that the rotating speed of ball mill is in the step (1)
1400-2500rpm, when Ball-milling Time is 3-16 small, temperature of charge is controlled at 25-35 DEG C.
12. preparation method according to claim 8, which is characterized in that step with centrifugal separation centrifugal force in the step (1)
For 6000~48000 × g.
13. preparation method according to claim 8, which is characterized in that carbon containing electric conductor presoma is in the step (2)
Polyacrylic acid, polyimides, phenolic resin, epoxy resin, glucose, graphene oxide, graphene, carbon nanotubes, organosilicon
One or more of oxygen alkane, polysiloxane, polysiloxane and paraxylene cross-linking products, silicones.
14. preparation method as claimed in claim 8, which is characterized in that the organic carbon source presoma in the step (3) is coal
One or more of pitch, asphalt, mesophase pitch, coal tar, thermoplastic resin.
15. preparation method as claimed in claim 8, which is characterized in that step (3) the temperature of charge control is in 100-250
DEG C, organic carbon source presoma is soft state or molten condition, and the kneading time is 1-4h.
16. preparation method as claimed in claim 8, which is characterized in that the hot pressing in the step (4) uses hot moulding or heat
Roll-in, hot pressing temperature are controlled more than organic carbon source presoma softening point temperature.
17. preparation method as claimed in claim 8, which is characterized in that isostatic pressed in the step (5) is isostatic cool pressing,
Any one in warm isostatic pressed or hot isostatic pressing, pressure were controlled in 10-250Mpa, dwell time 3-30 minute.
18. preparation method according to claim 8, which is characterized in that inert atmosphere is argon gas, nitrogen in the step (6)
One kind in gas, helium and argon hydrogen gaseous mixture.
19. preparation method as claimed in claim 8, which is characterized in that calcining heat is 600-1200 in the step (6)
DEG C, when the time is 0.5-8 small.
20. preparation method as claimed in claim 8, which is characterized in that the silicon substrate composite negative pole material of gained in the step (6)
Expect for spherical or random polygon, median particle diameter is 5-15 μm.
21. a kind of negative electrode of lithium ion battery, which is characterized in that include the silicon substrate Compound Negative any one of claim 1-7
Pole material.
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