CN105070894A - Porous silicon-based composite anode material for lithium ion battery and preparation method and application - Google Patents
Porous silicon-based composite anode material for lithium ion battery and preparation method and application Download PDFInfo
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- CN105070894A CN105070894A CN201510464295.2A CN201510464295A CN105070894A CN 105070894 A CN105070894 A CN 105070894A CN 201510464295 A CN201510464295 A CN 201510464295A CN 105070894 A CN105070894 A CN 105070894A
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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
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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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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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a porous silicon-based composite anode material for a lithium ion battery. The anode material is in a capsule structure; a capsule core is prepared from amorphous porous silicon; a capsule wall is prepared from a conductive carbon material; the particle sizes of the amorphous porous silicon are 10-300nm; the pore diameters of the amorphous porous silicon are 0.5-100nm; and the thickness of the capsule wall is 0.5-10 microns. The porous silicon-based composite anode material for the lithium ion battery provided by the invention is high in specific capacitance capacity, low in expansion, high in compaction density, good in processability, simple in process, friendly to environment and free of pollution.
Description
Technical field
The invention belongs to lithium ion battery negative material and electrochemical field, be specifically related to a kind of porous silicon-base composite negative pole material and preparation method thereof, and the lithium ion battery using this negative material to prepare.
Background technology
Lithium ion battery has the advantages such as energy density is large, self discharge is little, memory-less effect, operating voltage range are wide, long service life, non-environmental-pollution, is the main electrical source of power of current new-energy automobile.The crucial electrode material of lithium ion battery is the final deciding factor of battery performance, and wherein the raising of negative material to performance of lithium ion battery plays vital effect.And conventional graphite cathode specific capacity is close to the theoretical value of 372mAh/g, be difficult to the space having lifting again, so exploitation high-performance novel electrode material becomes study hotspot.
Silicon has the theoretical specific capacity (4200mAh/g) of superelevation and lower de-lithium current potential (<0.5V), and the voltage platform of silicon is a little more than graphite, and when charging, difficulty causes surface to analyse lithium, and security performance is better.Silicon becomes one of potential selection of richness of lithium ion battery carbon back negative pole upgrading.But silicon also has shortcoming as lithium ion battery negative material:
(1) easily there is volumetric expansion and contraction in silicon materials, affects electric cycle performance:
Silicon is semi-conducting material, the conductivity of self is lower, in electrochemistry cyclic process, the embedding of lithium ion and deviate to make material volume that the Swelling and contraction of more than 300% occurs, the mechanicals efforts produced can make material efflorescence gradually, causes structure collapses, finally causes electrode active material and collector to depart from, lose electrical contact, cause cycle performance of battery greatly to reduce;
(2) in use procedure, silicon materials are perishable, capacity attenuation:
Due to the bulk effect of silicon materials, be difficult in the electrolytic solution form stable solid electrolyte interface (SEI) film, along with the destruction of electrode structure, constantly form new SEI film at the silicon face exposed, exacerbate corrosion and the capacity attenuation of silicon.
CN103531760 discloses a kind of yolk-eggshell structural porous silicon-carbon complex microsphere and preparation method thereof, and the microballoon core that it provides is porous sub-micron silicon ball, and diameter is 400 ~ 900nm, shell is porous carbon, thickness is 10 ~ 60nm, and cavity inside diameter is 800 ~ 1400nm, and its preparation method is with SiO
2for core, to carry out carbon source coated, is fired into the SiO that porous carbon is coated
2powder, then by alkali treatment part SiO
2obtain the porous carbon coated Si O of yolk-eggshell structure
2powder, then by magnesiothermic reduction and HF process by SiO
2be reduced to silica flour, obtain the silicon-carbon complex microsphere of the coated porous silicon of porous carbon of yolk-eggshell structure, the method preparation section is complicated, the more difficult control of cavity inside diameter, although give silicon certain expansion space in addition, silicon grain carbon is coated not fine and close, conductivity is poor, unfavorable to its circulation for a long time.
Therefore, develop a kind of technique simple, excellent performance and the preparation method of eco-friendly amorphous nano porous silicon-base composite negative pole material are the important research directions of field of lithium ion battery.
Summary of the invention
For the deficiencies in the prior art, an object of the present invention is to provide a kind of lithium ion battery porous silicon-base composite negative pole material, and described negative material is capsule structure, and capsule-core is noncrystalline, porous silicon, and cyst wall is conductive carbon material.
The particle diameter of described noncrystalline, porous silicon is 10 ~ 300nm, such as 20nm, 50nm, 80nm, 120nm, 150nm, 180nm, 200nm, 240nm, 260nm, 280nm etc., the aperture of noncrystalline, porous silicon is 0.5-100nm, such as 1nm, 10nm, 30nm, 40nm, 55nm, 70nm, 90nm, 240nm etc.;
The thickness of described cyst wall is 0.5 ~ 10 μm, such as 0.8 μm, 2 μm, 4 μm, 6 μm, 7 μm, 9 μm etc.
Well known to a person skilled in the art, in lithium ion battery, the increase of silicone content can improve the ratio capacitance of lithium ion battery, but corresponding dilation effect can be brought, the present invention is by the lithium ion battery porous silicon-base composite negative pole material of design capsule structure, while combining silicon carbon material advantage, by capsule-core is set to noncrystalline, porous silicon, it is made to have larger specific area and abundant pore passage structure, effectively alleviate the volumetric expansion blockage effect of silicon in charge and discharge process, improve the combination property of material; In addition, arranging of cyst wall can avoid nano particle to reunite in cyclic process, intercept silicon directly contacts with electrolyte, greatly improves material circulation performance and efficiency first.And the reduction that whether simultaneously can obtain desirable ratio capacitance and volumetric expansion blockage effect is also determined to the selection in noncrystalline, porous silicon particle diameter and aperture; The setting of wall thickness is determined and can obtain firm capsule structure and desirable ratio capacitance.
Noncrystalline, porous silicon containing 5 ~ 60wt% in negative material of the present invention, the conductive carbon material of 40 ~ 95wt%, the mass percent sum of described noncrystalline, porous silicon and conductive carbon material is 100wt%.
Preferably, the median particle diameter of described negative material is 1 ~ 30 μm, such as 2 μm, 6 μm, 12 μm, 15 μm, 22 μm, 26 μm etc., preferably 2 ~ 20 μm, preferably 4 ~ 15 μm further.
Preferably, the specific area of described negative material is 1 ~ 20m
2/ g, such as 3m
2/ g, 6m
2/ g, 13m
2/ g, 18m
2/ g etc., preferably 2 ~ 10m
2/ g.
Preferably, the powder body compacted density of described negative material is 0.5 ~ 2.5g/cm
3, such as 0.8g/cm
3, 1g/cm
3, 1.1g/cm
3, 1.6g/cm
3, 2g/cm
3, 2.3g/cm
3deng, preferably 0.8 ~ 2g/cm
3.
Two of object of the present invention is the preparation method providing a kind of lithium ion battery porous silicon-base composite negative pole material as described in one of object, comprises the steps:
(1) get silicon alloy raw material Si-M, carry out extra-fine grinding, obtain silicon alloy particle;
(2) etch silicon alloying pellet, removing metallic element wherein, obtains noncrystalline, porous silicon grain;
(3) by noncrystalline, porous silicon and carbon source material homogeneous phase compound, negative material presoma is obtained;
(4) negative material presoma is carried out mechanical fusion, after sintering, obtain porous silicon-base composite negative pole material.
Step (1) described silicon alloy raw material Si-M is the combination of any a kind or at least 2 kinds in crystalline silicon alloy Si-M or amorphous silicon alloy Si-M, and the metallic element M in described silicon alloy raw material is selected from aluminium, titanium, nickel, tin, tungsten, iron, copper, manganese, cobalt, germanium, zinc, magnesium, any a kind or at least 2 kinds of combinations of sowing in metal simple-substance.
Preferably, described extra-fine grinding is selected from any a kind in dry ball milling or wet ball grinding.
Preferably, described ball-grinding machine is selected from any a kind in high-speed stirred mill, planetary ball mill, tube mill, type taper grinder, rod mill and sand mill, preferred planetary ball mill.
Preferably, the material of the ball milling pearl in described mechanical milling process is selected from stainless steel, agate, pottery, zirconia, aluminium oxide, any a kind in carbide alloy.
Preferably, the median particle diameter of described silicon alloy particle is 0.1 ~ 100 μm, such as 2 μm, 6 μm, 12 μm, 25 μm, 42 μm, 56 μm, 72 μm, 87 μm, 95 μm etc., preferably 0.5 ~ 50 μm, more preferably 1 ~ 15 μm.
The ball milling pearl diameter of described dry ball milling is 0.1 ~ 20mm, and ratio of grinding media to material is (10 ~ 200): 1; Rotational speed of ball-mill is 100 ~ 3000rpm, and Ball-milling Time is 1 ~ 100h.
Preferably, the ball milling pearl diameter of described wet ball grinding is 0.01 ~ 20mm, and ratio of grinding media to material is (10 ~ 200): 1, and rotating speed is 100 ~ 3000rpm, and Ball-milling Time is 1 ~ 50h.
Preferably, described wet ball grinding solvent for use is organic solvent and/or water.
Preferably, described organic solvent is the combination of any a kind or at least 2 kinds in oxolane, acid amides, alcohol and ketone, the combination of any a kind or at least 2 kinds in preferred oxolane, dimethylacetylamide, C1-C6 alcohol and C3-C8 ketone.
Preferably, described C1-C6 alcohol is methyl alcohol, ethanol, ethylene glycol, propyl alcohol, isopropyl alcohol, 1,2-PD, 1, ammediol, glycerol, n-butanol, 1, the combination of any a kind or at least 2 kinds in 2-butanediol, 1,3-BDO, BDO, n-amyl alcohol and 2-hexanol; Described C3-C8 ketone is the combination of any a kind or at least 2 kinds in acetone, methyl ethyl ketone, methyl propyl ketone, 1-METHYLPYRROLIDONE, ethyl propyl ketone, methyl butyl ketone, ethyl n-butyl ketone, methyl amyl ketone and methyl hexyl ketone.
Step (2) described etching is acid etch, is specially: be immersed in by silicon alloy particle in the first etching acid solution, stirs, etching metallic element M; Transfer them in the second etching acid solution afterwards, stir, etching metal oxide;
Preferably, described first etching acid is selected from the more active acid can reacted with metallic element M, the combination of any a kind or at least 2 kinds in preferred hydrochloric acid, nitric acid, nitrous acid, sulfuric acid, sulfurous acid, carbonic acid, boric acid, phosphoric acid, hydrofluoric acid, hydrogen cyanide, perchloric acid, acetic acid, benzoic acid, selenic acid;
Preferably, described second etching acid be can with the more active acid of reactive metal oxide, the combination of any a kind or at least 2 kinds preferably in hydrochloric acid, nitric acid, nitrous acid, sulfuric acid, sulfurous acid, carbonic acid, boric acid, phosphoric acid, hydrofluoric acid, hydrogen cyanide, perchloric acid, acetic acid, benzoic acid, selenic acid;
Preferably, described first etching acid solution and second etching acid solution in solvent independently selected from being water and/or organic solvent;
Preferably, described organic solvent is the combination of any a kind or at least 2 kinds in oxolane, acid amides, alcohol and ketone; 1 kind preferably in oxolane, dimethylacetylamide, C1-C6 alcohol and C3-C8 ketone or the combination of at least 2 kinds;
Preferably, described C1-C6 alcohol is methyl alcohol, ethanol, ethylene glycol, propyl alcohol, isopropyl alcohol, 1,2-PD, 1, ammediol, glycerol, n-butanol, 1, the combination of any a kind or at least 2 kinds in 2-butanediol, 1,3-BDO, BDO, n-amyl alcohol and 2-hexanol; Described C3-C8 ketone is the combination of in acetone, methyl ethyl ketone, methyl propyl ketone, 1-METHYLPYRROLIDONE, ethyl propyl ketone, methyl butyl ketone, ethyl n-butyl ketone, methyl amyl ketone and methyl hexyl ketone a kind or at least 2 kinds.
The composite amorphous state porous silicon of described step (3) described homogeneous phase is 1:2 ~ 1:20 with the mass ratio of conduction carbon source;
Preferably, described homogeneous phase compound is preferably solid phase compound or liquid phase compound;
Preferably, the processing step of described solid phase compound is: the described non-carbon source being 5 ~ 20 μm through porous silicon particle and particle diameter mixed, and mixing quality is than being 1:2 ~ 1:20, then VC mixer is placed in, regulating frequency 5 ~ 50Hz, mixes at least 30min, obtains noncrystalline, porous silicon grain;
Preferably, the processing step of described liquid phase compound is: the described non-carbon source being 5 ~ 20 μm through porous silicon particle and particle diameter mixed, and mixing quality, than being 1:2 ~ 1:20, is dispersed in water or organic solvent, dry, obtains noncrystalline, porous silicon grain;
Preferably, described carbon source material is the combination of any a kind or at least 2 kinds in alkanes, hydro carbons, alkene class, phenols, the arene derivative of 1 ~ 3 ring, polymer, carbohydrate, organic acid, resinae and macromolecular material, is preferably the combination of in methane, ethane, ethene, phenol, pitch, epoxy resin, phenolic resins, furfural resin, Lauxite, polyvinyl alcohol, polyvinyl chloride, polyethylene glycol, poly(ethylene oxide), Kynoar, acrylic resin and polyacrylonitrile a kind or at least 2 kinds.
The described mechanical fusion processing step of step (4) is:
Negative material presoma is added in fusion machine, adjusting rotary speed is 500 ~ 3000rpm, cutter gap width is 0.01 ~ 1cm, merge at least 0.25h, then be placed in reactor, pass into protective gas, be warming up to 400 DEG C ~ 900 DEG C, be cooled to room temperature after insulation 0.5 ~ 10h, obtain described step (4) porous silicon-base composite negative pole material;
Preferably, described protective gas is the combination of any a kind or at least 2 kinds in nitrogen, helium, neon, argon gas;
Preferably, described reactor is vacuum furnace, box type furnace, rotary furnace, roller kilns, pushed bat kiln or tube furnace.
Three of object of the present invention is to provide a kind of lithium ion battery, lithium ion battery porous silicon-base composite negative pole material described one of for the purpose of described lithium ion battery negative material.
Compared with prior art, the present invention has following beneficial effect:
(1) the present invention is by the lithium ion battery porous silicon-base composite negative pole material of design capsule structure, while combining silicon carbon material advantage, by capsule-core is set to noncrystalline, porous silicon, it is made to have larger specific area and abundant pore passage structure, effectively alleviate the volumetric expansion blockage effect of silicon in charge and discharge process, the combination property (500 circulation volume conservation rates are more than 93%) that improve material and efficiency (>92%) first; And the reduction that whether simultaneously can obtain desirable ratio capacitance and volumetric expansion blockage effect is also determined to the selection in noncrystalline, porous silicon particle diameter and aperture; The setting of wall thickness is determined and can obtain firm capsule structure and desirable ratio capacitance;
(2) lithium ion battery porous silicon-base composite negative pole material ratio capacitance capacity provided by the invention is high, and expand low, compacted density is high, and processing characteristics is good, technique is simple, and environmental friendliness is pollution-free.
Accompanying drawing explanation
Fig. 1 is scanning electron microscopy (SEM) figure of porous silicon-base composite negative pole material prepared by embodiment 1;
Fig. 2 is the XRD figure of porous silicon-base composite negative pole material prepared by embodiment 1;
Fig. 3 is the first charge-discharge curve of porous silicon-base composite negative pole material prepared by embodiment 1, and as seen from the figure, this material first charge-discharge capacity is higher.
Fig. 4 is the cycle performance curve of porous silicon-base composite negative pole material prepared by embodiment 1.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand, described embodiment is only help to understand the present invention, should not be considered as concrete restriction of the present invention.
Embodiment 1
A preparation method for lithium ion battery porous silicon-base composite negative pole material, comprises the steps:
(1) by median particle diameter be the Si-Fe alloy powder of 10 μm and the hardened steel ball of 3mm, after mixing by ball material mass ratio 100:1, load in the high energy ball mill of the stainless cylinder of steel of 5L, then argon shield gas is passed into, high-energy ball milling 100h under rotating speed is 500r/min condition, obtains Antaciron particle;
(2) join in 10wt%HCl solution slowly by Antaciron particle, Keep agitation 15h, while carrying out etching processing, the metal Fe in removing Antaciron particle, makes material form pore space structure, then carries out cleaning, suction filtration and vacuumize; Again dried material is joined in 10wt%HF solution slowly afterwards, Keep agitation 10h, further etching processing, meanwhile, the oxide in removing Antaciron particle, makes material surface form micropore, then carry out cleaning, suction filtration and vacuumize, obtain noncrystalline, porous silicon grain;
(3) by noncrystalline, porous silicon grain and particle diameter be 3 μm phenolic resins in mass ratio 30:60 carry out proportioning, mix and be placed in VC mixer, regulating frequency is 30Hz, mixing 60min, obtain negative material presoma;
(4) negative material presoma is added in fusion machine, adjusting rotary speed is 2000rpm, cutter gap width is 0.1cm, merge 2h, then be placed in high temperature box furnace, pass into nitrogen protection gas, be warming up to 750 DEG C, be cooled to room temperature after insulation 5h, obtain porous silicon-base composite negative pole material; Described porous silicon-base composite negative pole material median particle diameter is 12 μm; The particle diameter of capsule-core noncrystalline, porous silicon is 50nm, and aperture is 5nm, and wall thickness is 5 μm;
Fig. 1 is scanning electron microscopy (SEM) figure of porous silicon-base composite negative pole material prepared by embodiment 1;
Fig. 2 is the XRD figure of porous silicon-base composite negative pole material prepared by embodiment 1; Can be observed from figure, cracking carbon and the more weak diffraction maximum of nano-silicon, and peak is wider, can be judged this mainly because cracking carbon and nano-silicon are all the reasons of amorphous structure;
Fig. 3 is the first charge-discharge curve of porous silicon-base composite negative pole material prepared by embodiment 1, and as seen from the figure, the first charge-discharge capacity of porous silicon-base composite negative pole material prepared by embodiment 1 is higher;
Fig. 4 is the cycle performance curve of porous silicon-base composite negative pole material prepared by embodiment 1, and as seen from the figure, porous silicon-base composite negative pole material prepared by embodiment 1 has excellent cycle performance, and the 500 weeks capability retentions that circulate are 93.1%.
Embodiment 2
A preparation method for lithium ion battery porous silicon-base composite negative pole material, comprises the steps:
(1) be that the Si-Ti alloy powder of 30 μm joins in acetone solvent by median particle diameter, afterwards with the zirconium ball of 0.3mm, after mixing by ball material mass ratio 100:1, load ball milling cavity, then argon shield gas is passed into, under rotating speed is 2000r/min condition after ball milling 50h, obtain silicotitanium particle;
(2) silicotitanium particle is joined 10wt%HNO slowly
3in solution, Keep agitation 15h, while carrying out etching processing, the Titanium in removing silicotitanium particle, makes material form pore space structure, then carries out cleaning, suction filtration and vacuumize; Again dried material is joined in 10wt%HF solution slowly afterwards, Keep agitation 10h, further etching processing, meanwhile, the oxide in removing silicotitanium particle, makes material surface form micropore, then carry out cleaning, suction filtration and vacuumize, obtain noncrystalline, porous silicon grain;
(3) by noncrystalline, porous silicon grain and particle diameter be 3 μm polyvinyl alcohol in mass ratio 5:95 carry out proportioning, be then dissolved in ethanol, vacuumize, obtain negative material presoma;
(4) be added in fusion machine by negative material presoma, adjusting rotary speed is 500rpm, and cutter gap width is 1cm, merge 0.25h, be then placed in box type furnace, pass into nitrogen protection gas, be warming up to 400 DEG C, be cooled to room temperature after insulation 10h, obtain porous silicon-base composite negative pole material; Described porous silicon-base composite negative pole material median particle diameter is 30 μm; The particle diameter of capsule-core noncrystalline, porous silicon is 10nm, and aperture is 0.5nm, and wall thickness is 10 μm.
Embodiment 3
A preparation method for lithium ion battery porous silicon-base composite negative pole material, comprises the steps:
(1) be that the Si-Cu-Fe alloy powder of 80 μm joins in alcohol solvent by median particle diameter, afterwards with 0.01mm zirconium ball, after mixing by ball material mass ratio 200:1, load ball milling cavity, then argon shield gas is passed into, under rotating speed is 3000r/min condition after ball milling 1h, obtain copper silicon ferroalloy particles;
(2) copper silicon ferroalloy particles is joined in 10wt%HCl solution slowly, Keep agitation 15h, while carrying out etching processing, the metal Fe in removing precursor one and Ni metal, make material form pore space structure, then carry out cleaning, suction filtration and vacuumize; Again dried material is joined in 10wt%HF solution slowly afterwards, Keep agitation 10h, further etching processing, meanwhile, the oxide in removing copper silicon ferroalloy particles, makes material surface form micropore, then carry out cleaning, suction filtration and vacuumize, obtain noncrystalline, porous silicon grain;
(3) by noncrystalline, porous silicon grain and particle diameter be 20 μm pitch in mass ratio 5:100 carry out proportioning, mix and be placed in VC mixer, regulating frequency is 10Hz, mixing 120min, obtain negative material presoma;
(4) be added in fusion machine by negative material presoma, adjusting rotary speed is 3000rpm, and cutter gap width is 0.01cm, merge 1h, be then placed in box type furnace, pass into nitrogen protection gas, be warming up to 900 DEG C, be cooled to room temperature after insulation 0.5h, obtain porous silicon-base composite negative pole material; Described porous silicon-base composite negative pole material median particle diameter is 20 μm; The particle diameter of capsule-core noncrystalline, porous silicon is 300nm, and aperture is 100nm, and wall thickness is 8 μm.
Embodiment 4
A preparation method for lithium ion battery porous silicon-base composite negative pole material, comprises the steps:
(1) by median particle diameter be the Si-Al alloy powder of 1 μm and the hardened steel ball of 0.1mm, load after mixing by ball material mass ratio 100:1 in high energy ball mill, then pass into argon shield gas, high-energy ball milling 60h under rotating speed is 3000r/min condition, obtains silicon-aluminum particle;
(2) join in 10wt%HCl solution slowly by silicon-aluminum particle, Keep agitation 15h, while carrying out etching processing, the metallic aluminium in removing silicon-aluminum particle, makes material form pore space structure, then carries out cleaning, suction filtration and vacuumize; Afterwards dried material is joined in 10wt%HF solution slowly, Keep agitation 10h, further etching processing, meanwhile, the oxide in removing silicon-aluminum particle, makes material surface form micropore, then carry out cleaning, suction filtration and vacuumize, obtain noncrystalline, porous silicon grain;
(3) by noncrystalline, porous silicon grain and particle diameter be 1 μm of citric acid in mass ratio 20:80 carry out proportioning, be distributed in propanol solvent, dry, obtain negative material presoma;
(4) negative material presoma is added in fusion machine, adjusting rotary speed is 2000rpm, cutter gap width is 0.5cm, merge 2h, then be placed in high temperature box furnace, pass into nitrogen protection gas, be warming up to 600 DEG C, be cooled to room temperature after insulation 2h, obtain porous silicon-base composite negative pole material; Described porous silicon-base composite negative pole material median particle diameter is 1 μm; The particle diameter of capsule-core noncrystalline, porous silicon is 30nm, and aperture is 0.5nm, and wall thickness is 0.5 μm.
Comparative example 1
Be not carry out step (2) with the difference of embodiment 1.
Comparative example 2
Be that the time of step (1) high-energy ball milling is 20h with the difference of embodiment 1, step (3) silicon and particle diameter be 3 μm phenolic resins in mass ratio 30:90 carry out proportioning.Porous silicon-base composite negative pole material median particle diameter prepared by comparative example is 15 μm; The particle diameter of capsule-core noncrystalline, porous silicon is 350nm, and aperture is 7nm, and wall thickness is 12 μm;
Performance test:
The negative material that embodiment and comparative example provide is prepared battery, and concrete steps are:
By negative material, conductive agent and binding agent in mass ratio 94:1:5 mixed dissolution in a solvent, control solid content 50%, be coated in copper foil current collector, vacuum drying, obtained cathode pole piece; LiPF6/EC+DMC+EMC (v/v=1:1:1) electrolyte of the tertiary cathode pole piece then prepared by traditional maturation process, 1mol/L, Celgard2400 barrier film, shell adopt conventional production process to assemble 18650 cylinder cells;
On the Jin Nuo Electronics Co., Ltd. LAND battery test system of Wuhan, the charge-discharge performance of the cylindrical battery of test preparation, test condition is: normal temperature, and 0.2C constant current charge-discharge, charging/discharging voltage is limited in 2.75 ~ 4.2V.
Test result is in table 1:
The performance test results of table 1 embodiment and comparative example
From table 1, adopt the porous silicon-base composite negative pole material that described in the application prepared by method, the low (2 ~ 4m of specific area
2/ g), the high (1.6 ~ 1.8g/cm of compacted density
3) discharge capacity is greater than 1000mAh/g, initial coulomb efficiency is greater than 92%, circulates 500 weeks capability retentions all more than 93%; And comparative example 1 does not carry out porous silicon hole forming step, discharge capacity and the first charge-discharge efficiency of the material obtained are low, and efficiency only has 79.5% first, and the 500 weeks capability retentions that circulate only reach 84.3%; And comparative example 2 have adjusted the size of lithium ion battery porous silicon-base composite negative pole material porous silicon capsule-core and cyst wall, find that its 500 circulation volume conservation rates obviously decline, the negative material that coulombic efficiency does not have the application to provide yet first does very well.
Applicant states, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, namely do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of auxiliary element, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (9)
1. a lithium ion battery porous silicon-base composite negative pole material, is characterized in that, described negative material is capsule structure, and capsule-core is noncrystalline, porous silicon, and cyst wall is conductive carbon material;
The particle diameter of described noncrystalline, porous silicon is 10 ~ 300nm, and the aperture of noncrystalline, porous silicon is 0.5 ~ 100nm;
The thickness of described cyst wall is 0.5 ~ 10 μm.
2. negative material as claimed in claim 1, is characterized in that, the noncrystalline, porous silicon containing 5 ~ 60wt% in described negative material, the conductive carbon material of 40 ~ 95wt%;
Preferably, the median particle diameter of described negative material is 1 ~ 30 μm, preferably 2 ~ 20 μm, preferably 4 ~ 15 μm further;
Preferably, the specific area of described negative material is 1 ~ 20m
2/ g, preferably 2 ~ 10m
2/ g;
Preferably, the powder body compacted density of described negative material is 0.5 ~ 2.5g/cm
3, preferably 0.8 ~ 2g/cm
3.
3. a lithium ion battery preparation method for porous silicon-base composite negative pole material as claimed in claim 1 or 2, it is characterized in that, described method comprises the steps:
(1) get silicon alloy raw material Si-M, carry out extra-fine grinding, obtain silicon alloy particle;
(2) etch silicon alloying pellet, removing metallic element wherein, obtains noncrystalline, porous silicon grain;
(3) by noncrystalline, porous silicon and carbon source material homogeneous phase compound, negative material presoma is obtained;
(4) negative material presoma is carried out mechanical fusion, after sintering, obtain porous silicon-base composite negative pole material.
4. method as claimed in claim 3, it is characterized in that, step (1) described silicon alloy raw material Si-M is the combination of any a kind or at least 2 kinds in crystalline silicon alloy Si-M or amorphous silicon alloy Si-M, and the metallic element M in described silicon alloy raw material is selected from aluminium, titanium, nickel, tin, tungsten, iron, copper, manganese, cobalt, germanium, zinc, magnesium, any a kind or at least 2 kinds of combinations of sowing in metal simple-substance;
Preferably, described extra-fine grinding is selected from any a kind in dry ball milling or wet ball grinding;
Preferably, described ball-grinding machine is selected from any a kind in high-speed stirred mill, planetary ball mill, tube mill, type taper grinder, rod mill and sand mill, preferred planetary ball mill;
Preferably, the material of the ball milling pearl in described mechanical milling process is selected from stainless steel, agate, pottery, zirconia, aluminium oxide, any a kind in carbide alloy;
Preferably, the median particle diameter of described silicon alloy particle is 0.1 ~ 100 μm, preferably 0.5 ~ 50 μm, more preferably 1 ~ 15 μm.
5. method as claimed in claim 4, it is characterized in that, the ball milling pearl diameter of described dry ball milling is 0.1 ~ 20mm, and ratio of grinding media to material is (10 ~ 200): 1; Rotational speed of ball-mill is 100 ~ 3000rpm, and Ball-milling Time is 1 ~ 100h;
Preferably, the ball milling pearl diameter of described wet ball grinding is 0.01 ~ 20mm, and ratio of grinding media to material is (10 ~ 200): 1, and rotating speed is 100 ~ 3000rpm, and Ball-milling Time is 1 ~ 50h;
Preferably, described wet ball grinding solvent for use is organic solvent and/or water;
Preferably, described organic solvent is the combination of any a kind or at least 2 kinds in oxolane, acid amides, alcohol and ketone, the combination of any a kind or at least 2 kinds in preferred oxolane, dimethylacetylamide, C1-C6 alcohol and C3-C8 ketone;
Preferably, described C1-C6 alcohol is methyl alcohol, ethanol, ethylene glycol, propyl alcohol, isopropyl alcohol, 1,2-PD, 1, ammediol, glycerol, n-butanol, 1, the combination of any a kind or at least 2 kinds in 2-butanediol, 1,3-BDO, BDO, n-amyl alcohol and 2-hexanol; Described C3-C8 ketone is the combination of any a kind or at least 2 kinds in acetone, methyl ethyl ketone, methyl propyl ketone, 1-METHYLPYRROLIDONE, ethyl propyl ketone, methyl butyl ketone, ethyl n-butyl ketone, methyl amyl ketone and methyl hexyl ketone.
6. the method as described in one of claim 3 ~ 5, is characterized in that, step (2) described etching is acid etch, is specially: be immersed in by silicon alloy particle in the first etching acid solution, stirs, etching metallic element M; Transfer them in the second etching acid solution afterwards, stir, etching metal oxide;
Preferably, described first etching acid is selected from the more active acid can reacted with metallic element M, the combination of any a kind or at least 2 kinds in preferred hydrochloric acid, nitric acid, nitrous acid, sulfuric acid, sulfurous acid, carbonic acid, boric acid, phosphoric acid, hydrofluoric acid, hydrogen cyanide, perchloric acid, acetic acid, benzoic acid, selenic acid;
Preferably, described second etching acid be can with the more active acid of reactive metal oxide, the combination of any a kind or at least 2 kinds preferably in hydrochloric acid, nitric acid, nitrous acid, sulfuric acid, sulfurous acid, carbonic acid, boric acid, phosphoric acid, hydrofluoric acid, hydrogen cyanide, perchloric acid, acetic acid, benzoic acid, selenic acid;
Preferably, described first etching acid solution and second etching acid solution in solvent independently selected from being water and/or organic solvent;
Preferably, described organic solvent is the combination of any a kind or at least 2 kinds in oxolane, acid amides, alcohol and ketone; 1 kind preferably in oxolane, dimethylacetylamide, C1-C6 alcohol and C3-C8 ketone or the combination of at least 2 kinds;
Preferably, described C1-C6 alcohol is methyl alcohol, ethanol, ethylene glycol, propyl alcohol, isopropyl alcohol, 1,2-PD, 1, ammediol, glycerol, n-butanol, 1, the combination of any a kind or at least 2 kinds in 2-butanediol, 1,3-BDO, BDO, n-amyl alcohol and 2-hexanol; Described C3-C8 ketone is the combination of in acetone, methyl ethyl ketone, methyl propyl ketone, 1-METHYLPYRROLIDONE, ethyl propyl ketone, methyl butyl ketone, ethyl n-butyl ketone, methyl amyl ketone and methyl hexyl ketone a kind or at least 2 kinds.
7. the method as described in one of claim 3 ~ 6, is characterized in that, the mass ratio of the composite amorphous state porous silicon of step (3) described homogeneous phase and carbon source material is 1:2 ~ 1:20;
Preferably, described homogeneous phase compound is preferably solid phase compound or liquid phase compound;
Preferably, the processing step of described solid phase compound is: the described non-carbon source being 5 ~ 20 μm through porous silicon particle and particle diameter mixed, and mixing quality is than being 1:2 ~ 1:20, then VC mixer is placed in, regulating frequency 5 ~ 50Hz, mixes at least 30min, obtains noncrystalline, porous silicon grain;
Preferably, the processing step of described liquid phase compound is: the described non-carbon source being 5 ~ 20 μm through porous silicon particle and particle diameter mixed, and mixing quality, than being 1:2 ~ 1:20, is dispersed in water or organic solvent, dry, obtains noncrystalline, porous silicon grain;
Preferably, described carbon source material is the combination of any a kind or at least 2 kinds in alkanes, hydro carbons, alkene class, phenols, the arene derivative of 1 ~ 3 ring, polymer, carbohydrate, organic acid, resinae and macromolecular material, is preferably the combination of in methane, ethane, ethene, phenol, pitch, epoxy resin, phenolic resins, furfural resin, Lauxite, polyvinyl alcohol, polyvinyl chloride, polyethylene glycol, poly(ethylene oxide), Kynoar, acrylic resin and polyacrylonitrile a kind or at least 2 kinds.
8. the method as described in one of claim 3 ~ 7, is characterized in that, the described mechanical fusion processing step of step (4) is:
Negative material presoma is added in fusion machine, adjusting rotary speed is 500 ~ 3000rpm, cutter gap width is 0.01 ~ 1cm, merge at least 0.25h, then be placed in reactor, pass into protective gas, be warming up to 400 DEG C ~ 900 DEG C, be cooled to room temperature after insulation 0.5 ~ 10h, obtain described step (4) porous silicon-base composite negative pole material;
Preferably, described protective gas is the combination of any a kind or at least 2 kinds in nitrogen, helium, neon, argon gas;
Preferably, described reactor is vacuum furnace, box type furnace, rotary furnace, roller kilns, pushed bat kiln or tube furnace.
9. a lithium ion battery, is characterized in that, described lithium ion battery negative material is the lithium ion battery porous silicon-base composite negative pole material described in claim 1 or 2.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1891668A (en) * | 2005-07-08 | 2007-01-10 | 中国科学院物理研究所 | Carbon-silicon composite material with spherical nucleocapsid, and its preparing method and use |
| CN101297422A (en) * | 2005-10-27 | 2008-10-29 | 株式会社Lg化学 | Electrode active material for secondary battery |
| CN103238238A (en) * | 2010-10-22 | 2013-08-07 | 安普雷斯股份有限公司 | Composite structures containing high capacity porous active materials constrained in shells |
| CN104617269A (en) * | 2015-01-23 | 2015-05-13 | 深圳市贝特瑞新能源材料股份有限公司 | Silicon alloy composite anode material, preparation method and lithium ion battery |
-
2015
- 2015-07-31 CN CN201510464295.2A patent/CN105070894B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1891668A (en) * | 2005-07-08 | 2007-01-10 | 中国科学院物理研究所 | Carbon-silicon composite material with spherical nucleocapsid, and its preparing method and use |
| CN101297422A (en) * | 2005-10-27 | 2008-10-29 | 株式会社Lg化学 | Electrode active material for secondary battery |
| CN103238238A (en) * | 2010-10-22 | 2013-08-07 | 安普雷斯股份有限公司 | Composite structures containing high capacity porous active materials constrained in shells |
| CN104617269A (en) * | 2015-01-23 | 2015-05-13 | 深圳市贝特瑞新能源材料股份有限公司 | Silicon alloy composite anode material, preparation method and lithium ion battery |
Cited By (30)
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