CN102332571A - Silicon-carbon compound cathode material and manufacturing method thereof as well as lithium ion battery and cathode piece - Google Patents
Silicon-carbon compound cathode material and manufacturing method thereof as well as lithium ion battery and cathode piece Download PDFInfo
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- CN102332571A CN102332571A CN201110281768A CN201110281768A CN102332571A CN 102332571 A CN102332571 A CN 102332571A CN 201110281768 A CN201110281768 A CN 201110281768A CN 201110281768 A CN201110281768 A CN 201110281768A CN 102332571 A CN102332571 A CN 102332571A
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- 239000010406 cathode material Substances 0.000 title claims abstract description 36
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 27
- 229910001416 lithium ion Inorganic materials 0.000 title claims description 27
- 239000000463 material Substances 0.000 claims abstract description 26
- 239000002105 nanoparticle Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000002296 pyrolytic carbon Substances 0.000 claims abstract description 10
- 238000005530 etching Methods 0.000 claims abstract description 7
- 238000005507 spraying Methods 0.000 claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 4
- 239000003610 charcoal Substances 0.000 claims description 43
- 239000005543 nano-size silicon particle Substances 0.000 claims description 40
- 239000002245 particle Substances 0.000 claims description 36
- 239000002153 silicon-carbon composite material Substances 0.000 claims description 31
- 229920000642 polymer Polymers 0.000 claims description 21
- 239000007789 gas Substances 0.000 claims description 18
- 239000011261 inert gas Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 14
- 238000005229 chemical vapour deposition Methods 0.000 claims description 12
- 229910052786 argon Inorganic materials 0.000 claims description 11
- 238000003763 carbonization Methods 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 239000003595 mist Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000013459 approach Methods 0.000 claims description 8
- 238000009413 insulation Methods 0.000 claims description 8
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- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 239000011280 coal tar Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 5
- 229920001296 polysiloxane Polymers 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- 230000004888 barrier function Effects 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 229910021487 silica fume Inorganic materials 0.000 claims description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 235000011187 glycerol Nutrition 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 238000009423 ventilation Methods 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052710 silicon Inorganic materials 0.000 abstract description 5
- 239000010703 silicon Substances 0.000 abstract description 5
- 238000007599 discharging Methods 0.000 abstract description 4
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- 238000010000 carbonizing Methods 0.000 abstract 1
- 238000005453 pelletization Methods 0.000 abstract 1
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
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- 230000002950 deficient Effects 0.000 description 2
- 239000002070 nanowire Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
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- 238000013461 design Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a silicon-carbon compound cathode material and a manufacturing method thereof. The material has a nano/micro structure which is characterized in that the material mainly comprises micron-sized grains with surfaces covered by pyrolytic carbon; the micron-sized grains are composed of a plurality of nano-sized grains; and each of the nano-sized grains is a nano-sized silicon grain with the surface covered by a carbon layer. The manufacturing method of the silicon-carbon compound cathode material comprises an etching step, a carbon-layer covering step, a scattering step, a spraying pelletizing step and a carbonizing treatment step. The silicon-carbon compound cathode material prepared by using the method has a nano/micro structure, a first cycle efficiency over 85%, a first discharging capability over 1000mAh/g and a retention rate of 100 times cycle capacity over 90%.
Description
Technical field
The present invention relates to battery technology and new energy materials, particularly relate to a kind of silicon-carbon composite cathode material and manufacturing approach, lithium ion battery and negative plate.
Background technology
Fields such as electric motor car are more and more urgent to the demand of high-performance lithium ion battery.At present, with the commercialization lithium ion battery of graphite-like raw material of wood-charcoal material, because the low defectives such as (theoretical capacity 372mAh/g) of charcoal class negative pole specific capacity has seriously hindered further developing of capacity of lithium ion battery as negative material.The theoretical specific capacity of Si is up to 4200 mAh/g; It is the highest negative material of capacity; But because in the doff lithium process big change in volume can take place subsequently, thus cause efflorescence, the secondary agglomeration of material that active material is lost activity, make that the capacity attenuation of material is very fast; In addition, the change in volume in the doff lithium process also can make to lose closely between negative plate and the collector and electrically contact.Thereby can big capacity silicon cycle performance improve, and can just become this material the large-scale commercial applications key technologies for application.
Recently; Aspect the chemical property that improves high power capacity silicon; Forefathers have done a large amount of work, and nanometerization is to improve the effective way of these material cycle performances, yet nanometerization can not fundamentally solve expansion, efflorescence causes the defective that the internal resistance of cell increases, cycle performance worsens; Nano thin-film has high specific capacity, excellent cycle performance and high rate charge-discharge performance, but its effective active matter is less, and preparation condition is harsh; Nano wire and nanotube are effective to the expansion that suppresses charge and discharge process, but the polarization of the nano wire under high current density reinforcement, thereby have influenced the high rate performance and the cycle life of material.
Summary of the invention
Technical problem to be solved by this invention is: remedy the deficiency of prior art, propose a kind of silicon-carbon composite cathode material and manufacturing approach, anode plate for lithium ionic cell and lithium ion battery, this negative material capacity is high, cycle performance is good.
Technical problem of the present invention solves through following technical scheme:
A kind of silicon-carbon composite cathode material; Said material has nano-micro structure; Said nano-micro structure refers to: said material mainly is made up of the micron particles that the outside is coated with pyrolytic carbon; Said micron particles is made up of some nano-scale particles, and each said nano-scale particle is the silicon nanoparticle that the surface is coated with the charcoal layer.
Preferably, the mass fraction of carbon is 10-70% in the said material, and surplus is a nano-silicon, and the particle diameter of said nano-silicon is the 10-30 nanometer, and the particle diameter of said micron particles is the 10-30 micron.
Preferably, said pyrolytic carbon is made by polymer charcoal source, and said polymer charcoal source is a kind of in resin, pitch or the coal tar; The mist that said charcoal layer is made up of carbonaceous gas and inert gas makes through chemical vapour deposition (CVD), and said carbonaceous gas is C
3H
8, C
2H
4, C
6H
5CH
3, C
2H
2In a kind of, said inert gas is Ar or N
2, the volume ratio of carbonaceous gas and inert gas is 1:9 ~ 9:1.
A kind of method of silicon-carbon composite cathode material may further comprise the steps:
(1) etch step: nano-silicon is carried out surface etching treatment, obtain the nano-silicon powder;
(2) coat charcoal layer step: the nano silica fume surface coats the charcoal layer in said step (1), obtains the silicon-carbon compound particle.
(3) dispersion steps: polymer charcoal source is dissolved in the organic solvent, and obtaining concentration is the polymer charcoal source solution of 10-50wt%; In the solution of said polymer charcoal source, silicone content is 10-80wt% in the solution, obtains slurry with the silicon-carbon compound particle dispersed with stirring in the said step (2);
(4) mist projection granulating step: with the slip spraying of said step (3) gained, the vaporific particle that is sprayed falls into the solvent of boiling, obtains the micron order granular precursor after the filtration;
(5) carbonization treatment step: the resulting micron order granular precursor of said step (4) is carried out carbonization treatment make the described lithium ion battery of claim 1 and use silicon-carbon composite cathode material under nitrogen or argon shield atmosphere.
Preferably; Said step (1) is meant that it is the powerful 5-30min of stirring of HF solution of 1-10wt% that nano-silicon is placed concentration, filter then, with filter residue with the pH=7 of deionized water wash to filtrating; At last 50-80 ℃ of vacuumize more than 24 hours, promptly get the nano-silicon powder after the surface etch; Or
Nano-silicon is placed thionyl chloride solution, filters after 12-24 hour at 50-90 ℃ of dipping, then with the deionized water wash filter residue to the pH=7 that filtrates, at last 50-80 ℃ of vacuumize more than 24 hours, promptly get the nano-silicon powder after the surface etch.
Preferably; Said step (2) adopts chemical vapour deposition technique (Chemical Vapor Deposition, initialism are CVD), between 900 ℃-1200 ℃; Feed the mist that carbonaceous gas and inert gas are formed; Coat the charcoal layer on the nano-silicon surface, duration of ventilation is 30min-10h, and said carbonaceous gas is C
3H
8, C
2H
4, C
6H
5CH
3, C
2H
2In a kind of, said inert gas is Ar or N
2, the volume ratio of carbonaceous gas and inert gas is 1:9 ~ 9:1.
Preferably, the polymer charcoal source in the said step (3) is a kind of in resin, pitch or the coal tar; Said organic solvent is a kind of in methyl alcohol, ethanol, acetone, the n-hexane; The stirring intensity of said dispersed with stirring is 1000-3000rpm, and mixing time is 60-240min.
Preferably, the vaporific granular size of the ejection of slip described in the said step (4) is 10-30 μ m, and said solvent is glycerine, n-hexane or amylalcohol.
Preferably, the condition of carbonization treatment is in the said step (5): the programming rate with 1-20 ℃/min is heated to 300-400 ℃, behind the insulation 0.5-10h, is heated to 600-1000 ℃ with the programming rate of 1-20 ℃/min, behind the insulation 0.5-10h, cools off with stove.
A kind of lithium ion battery is used negative plate, comprises substrate, and is coated in suprabasil above-mentioned silicon-carbon composite cathode material.
A kind of lithium ion battery comprises battery container, electrode group and electrolyte, and electrode group and electrolyte are sealed in the battery container, and the electrode group comprises positive pole, barrier film and negative pole, and said negative pole is that above-mentioned lithium ion battery is used negative plate.
The beneficial effect of the present invention and prior art contrast is: silicon-carbon composite cathode material of the present invention has nano-micro structure; Each micron particles is made up of nano-scale particle; Each nano-scale particle is the silicon nanoparticle that the surface is coated with the charcoal layer, and the outer charcoal layer of silicon nanoparticle can be kept excellent electric contact, the raising conductivity between the semiconductor silicon, can also stop the nano-silicon stress that change in volume is brought in charge and discharge process; And the secondary agglomeration that stops single silicon grain to bring after maybe efflorescence; In addition, micron particles also is coated with pyrolytic carbon outward, and it is inner that this pyrolytic carbon can stop the solvation lithium ion to get into micron particles; The silicon-carbon composite cathode material of this kind structure has advantages such as capacity height, excellent cycle performance; Cycle efficieny is greater than 85% first, and discharge capacity can reach more than 1000 mAh/g first, and 100 circulation volume conservation rates are greater than 90%.
Description of drawings
The lithium ion battery of Fig. 1 embodiment of the invention is with the nano-micro structure sketch map of silicon-carbon composite cathode material;
The lithium ion battery of Fig. 2 embodiment of the invention is with the preparation flow figure of silicon-carbon composite cathode material.
Embodiment
The contrast accompanying drawing carries out detailed elaboration with the combination preferred embodiment to the present invention below.
The silicon-carbon composite cathode material of an embodiment; Said material has nano-micro structure, and said nano-micro structure refers to: said material mainly is made up of the micron particles that the outside is coated with pyrolytic carbon, and said micron particles is made up of some nano-scale particles; Each said nano-scale particle is the silicon nanoparticle that the surface is coated with the charcoal layer; Preferably, the particle diameter of said nano-silicon is the 10-30 nanometer, and the particle diameter of said micron particles is the 10-30 micron.
The method of the silicon-carbon composite cathode material of an embodiment may further comprise the steps:
(1) etch step: nano-silicon is carried out surface etching treatment, obtain the nano-silicon powder;
(2) coat charcoal layer step: the nano silica fume surface coats the charcoal layer in said step (1), obtains the silicon-carbon compound particle.
(3) dispersion steps: polymer charcoal source is dissolved in the organic solvent, and obtaining concentration is the polymer charcoal source solution of 10-50wt%; In the solution of said polymer charcoal source, silicone content is 10-80wt% in the solution, obtains slurry with the silicon-carbon compound particle dispersed with stirring in the said step (2);
(4) mist projection granulating step: with the slip spraying of said step (3) gained, the vaporific particle that is sprayed falls into the solvent of boiling, obtains the micron order granular precursor after the filtration;
(5) carbonization treatment step: the resulting micron order granular precursor of said step (4) is carried out charing handle and to make the described lithium ion battery of claim 1 and use silicon-carbon composite cathode material under nitrogen or argon shield atmosphere.
The lithium ion battery of an embodiment is used negative plate, comprises substrate, and is coated in suprabasil above-mentioned silicon-carbon composite cathode material.
The lithium ion battery of an embodiment comprises battery container, electrode group and electrolyte, and electrode group and electrolyte are sealed in the battery container, and the electrode group comprises positive pole, barrier film and negative pole, and said negative pole is that above-mentioned lithium ion battery is used negative plate.
In another embodiment, as shown in Figure 1, silicon-carbon composite cathode material; Have nano-micro structure, said nano-micro structure refers to: said material is made up of the micron particles that the outside is coated with pyrolytic carbon 3, and said micron particles is made up of some nano-scale particles; Each said nano-scale particle is the silicon nanoparticle 1 that the surface is coated with charcoal layer 2; Preferably, the mass fraction of carbon is 10-70% in the material, and surplus is a nano-silicon; The particle diameter of said nano-silicon is the 10-30 nanometer, and the particle diameter of said micron particles is the 10-30 micron.Preferably, pyrolytic carbon is made by polymer charcoal source, and said polymer charcoal source is a kind of in resin, pitch or the coal tar.Preferably, the mist that the charcoal layer is made up of carbonaceous gas and inert gas makes through chemical vapour deposition (CVD), and said carbonaceous gas is C
3H
8, C
2H
4, C
6H
5CH
3, C
2H
2In a kind of, said inert gas is Ar or N
2, the volume ratio of carbonaceous gas and inert gas is 1:9 ~ 9:1.
In another embodiment, as shown in Figure 2, the method for silicon-carbon composite cathode material may further comprise the steps:
(1) etch step: nano-silicon is carried out surface etching treatment, obtain the nano-silicon powder; Preferably; It is the powerful 5-30min of stirring of HF solution of 1-10wt% that nano-silicon is placed concentration, filter then, with filter residue with the pH=7 of deionized water wash to filtrating; At last 50-80 ℃ of vacuumize more than 24 hours, promptly get the nano-silicon powder after the surface etch; Or nano-silicon placed thionyl chloride solution, filter after 12-24 hour at 50-90 ℃ of dipping, then with the deionized water wash filter residue to the pH=7 that filtrates, at last 50-80 ℃ of vacuumize more than 24 hours, promptly get the nano-silicon powder after the surface etch.Further preferably; Employing is carried out surface etching treatment to commercial nano-silicon; The average grain diameter of nanometer Si is 30nm, and placing concentration to nano-silicon is the powerful 30min of stirring of HF solution of 5wt%, then with the powder after the centrifugal filtration repeatedly use deionized water wash to the PH that filtrates be 7; At last 60 ℃ of vacuumizes more than 24 hours, promptly get the nano-silicon powder after the surface etching treatment.
(2) coat charcoal layer step: the nano silica fume surface in step (1) coats the charcoal layer, obtains the silicon-carbon compound particle.Feed the mist that carbonaceous gas and inert gas are formed, coat the charcoal layer through the CVD method on the nano-silicon surface, preferably, the condition of CVD deposition is: between 900 ℃-1200 ℃, duration of ventilation is 30min-10h, and carbonaceous gas is C
3H
8, C
2H
4, C
6H
5CH
3, C
2H
2In a kind of, said inert gas is Ar or N
2, the volume ratio of carbonaceous gas and inert gas is 1:9 ~ 9:1.
(3) dispersion steps: polymer charcoal source is dissolved in the organic solvent, and obtaining concentration is the polymer charcoal source solution of 10-50wt%; In the solution of polymer charcoal source, silicone content is 10-80wt% in the solution, obtains slurry with the silicon-carbon compound particle dispersed with stirring in the step (2); Preferably, polymer charcoal source is a kind of in resin, pitch or the coal tar; Preferably, organic solvent is a kind of in methyl alcohol, ethanol, acetone, the n-hexane; Preferably, the stirring intensity of dispersed with stirring is 1000-3000rpm, and mixing time is 60-240min.Further preferably, phenolic resins is dispersed in the ethanolic solution, obtains the phenol resin solution that concentration is 10-50wt%; Secondly, the silicon-carbon compound particle of step (2) was put into solution stirring 2 hours, it is evenly spread in the phenol resin solution, silicone content is 20wt% in the solution, obtains slurry;
(4) mist projection granulating step: with the slip spraying of step (3) gained, the vaporific particle that is sprayed falls into the solvent of boiling, obtains the micron order granular precursor after the filtration; Preferably, the vaporific granular size of slip ejection is 10-30 μ m, and solvent is a kind of in glycerine, n-hexane or the amylalcohol.Further preferably, with the spraying of gained slip, the vaporific grain diameter that is sprayed is about 30 μ m, makes it fall into the n-hexane solvent granulation of boiling, obtains the micron order granular precursor after the filtration.
(5) carbonization treatment step: the resulting micron order granular precursor of step (4) is carried out carbonization treatment promptly make lithium ion battery and use silicon-carbon composite cathode material under nitrogen or argon shield atmosphere.Preferably, the condition of carbonization treatment is: the programming rate with 1-20 ℃/min is heated to 300-400 ℃, behind the insulation 0.5-10h, is heated to 600-1000 ℃ with the programming rate of 1-20 ℃/min, behind the insulation 0.5-10h, cools off with stove.Further preferably, the micron order granular precursor under argon shield atmosphere, is heated to 250 ℃ with the programming rate of 10 ℃/min; Behind the insulation 2h; Programming rate with 5 ℃/min is heated to 600 ℃, insulation 2h, carries out carbonization treatment, promptly obtains having the nano-micro structure silicon-carbon cathode material.Usually silicon-carbon composite cathode material is used for lithium ion battery.
In another embodiment, lithium ion battery is used negative plate, and the nano-micro structure silicon-carbon cathode material that above-mentioned arbitrary embodiment is prepared is coated on the Copper Foil, obtains negative plate.
In another embodiment, lithium ion battery comprises battery container, electrode group and electrolyte, and electrode group and electrolyte are sealed in the battery container, and the electrode group comprises positive pole, barrier film and negative pole, and wherein negative pole is that above-mentioned lithium ion battery is used negative plate.
The negative material Performance Detection: above-mentioned negative plate and metal lithium sheet are formed the electrochemistry embedding of half-cell test material/take off the lithium performance, and electrolyte is commercially available 1M LiPF
6/ EC+DMC solution.Utilize the Land battery test system that above-mentioned half-cell is at room temperature carried out the constant current charge-discharge performance test, charging and discharging currents density is 120mA/g, and the charging/discharging voltage scope is 0-1.5V.
The battery performance testing result: when under the 120mA/g multiplying power, discharging and recharging, the cycle efficieny first of present embodiment material is 86%, and reversible capacity is 1380mAh/g first; And present business-like CMS is at the about 305mAh/g of reversible capacity first of 74.4mA/g rate charge-discharge.In preceding 100 circulations, the capacity attenuation of each circulation of present embodiment is less than 0.1%, and promptly 100 circulation back capability retentions are higher than 90% (this material reversible capacity after 100 circulations is 1250mAh/g); But the capability retention of commercial CMS after 100 circulations is 84%.Test result shows that the present embodiment Si-C composite material has height ratio capacity and outstanding cycle performance.
Above content is to combine concrete preferred implementation to the further explain that the present invention did, and can not assert that practical implementation of the present invention is confined to these explanations.For the those of ordinary skill of technical field under the present invention, do not breaking away under the prerequisite of the present invention design, make some being equal to substitute or obvious modification, and performance or purposes are identical, all should be regarded as belonging to protection scope of the present invention.
Claims (11)
1. silicon-carbon composite cathode material; It is characterized in that: said material has nano-micro structure; Said nano-micro structure refers to: said material mainly is made up of the micron particles that the outside is coated with pyrolytic carbon; Said micron particles is made up of some nano-scale particles, and each said nano-scale particle is the silicon nanoparticle that the surface is coated with the charcoal layer.
2. silicon-carbon composite cathode material as claimed in claim 1 is characterized in that: the mass fraction of carbon is 10-70% in the said material, and surplus is a nano-silicon; The particle diameter of said nano-silicon is the 10-30 nanometer, and the particle diameter of said micron particles is the 10-30 micron.
3. according to claim 1 or claim 2 silicon-carbon composite cathode material, it is characterized in that: said pyrolytic carbon is made by polymer charcoal source, and said polymer charcoal source is a kind of in resin, pitch or the coal tar; The mist that said charcoal layer is made up of carbonaceous gas and inert gas makes through chemical vapour deposition (CVD), and said carbonaceous gas is C
3H
8, C
2H
4, C
6H
5CH
3, C
2H
2In a kind of, said inert gas is Ar or N
2, the volume ratio of carbonaceous gas and inert gas is 1:9 ~ 9:1.
4. the method for a silicon-carbon composite cathode material is characterized in that: may further comprise the steps:
(1) etch step: nano-silicon is carried out surface etching treatment, obtain the nano-silicon powder;
(2) coat charcoal layer step: the nano silica fume surface coats the charcoal layer in said step (1), obtains the silicon-carbon compound particle;
(3) dispersion steps: polymer charcoal source is dissolved in the organic solvent, and obtaining concentration is the polymer charcoal source solution of 10-50wt%; In the solution of said polymer charcoal source, silicone content is 10-80wt% in the solution, obtains slurry with the silicon-carbon compound particle dispersed with stirring in the said step (2);
(4) mist projection granulating step: with the slip spraying of said step (3) gained, the vaporific particle that is sprayed falls into the solvent of boiling, obtains the micron order granular precursor after the filtration;
(5) carbonization treatment step: the resulting micron order granular precursor of said step (4) is carried out carbonization treatment make the described lithium ion battery of claim 1 and use silicon-carbon composite cathode material under nitrogen or argon shield atmosphere.
5. the manufacturing approach of silicon-carbon composite cathode material as claimed in claim 4; It is characterized in that: said step (1) is meant that it is the powerful 5-30min of stirring of HF solution of 1-10wt% that nano-silicon is placed concentration; Filter then; Filter residue with the pH=7 of deionized water wash to filtrating, at last 50-80 ℃ of vacuumize more than 24 hours, is promptly got the nano-silicon powder after the surface etch; Or
Nano-silicon is placed thionyl chloride solution, filters after 12-24 hour at 50-90 ℃ of dipping, then with the deionized water wash filter residue to the pH=7 that filtrates, at last 50-80 ℃ of vacuumize more than 24 hours, promptly get the nano-silicon powder after the surface etch.
6. like the manufacturing approach of claim 4 or 5 described silicon-carbon composite cathode materials; It is characterized in that: said step (2) adopts chemical vapour deposition technique; Between 900 ℃-1200 ℃, feed the mist that carbonaceous gas and inert gas are formed, coat the charcoal layer on the nano-silicon surface; Duration of ventilation is 30min-10h, and said carbonaceous gas is C
3H
8, C
2H
4, C
6H
5CH
3, C
2H
2In a kind of, said inert gas is Ar or N
2, the volume ratio of carbonaceous gas and inert gas is 1:9 ~ 9:1.
7. like the manufacturing approach of claim 4 or 5 described silicon-carbon composite cathode materials, it is characterized in that: the polymer charcoal source in the said step (3) is a kind of in resin, pitch or the coal tar; Said organic solvent is a kind of in methyl alcohol, ethanol, acetone, the n-hexane; The stirring intensity of said dispersed with stirring is 1000-3000rpm, and mixing time is 60-240min.
8. like the manufacturing approach of claim 4 or 5 described silicon-carbon composite cathode materials, it is characterized in that: the vaporific granular size of the ejection of slip described in the said step (4) is 10-30 μ m, and said solvent is glycerine, n-hexane or amylalcohol.
9. like the manufacturing approach of claim 4 or 5 said a kind of silicon-carbon composite cathode materials; It is characterized in that: the condition of carbonization treatment is in the said step (5): the programming rate with 1-20 ℃/min is heated to 300-400 ℃; Behind the insulation 0.5-10h; Programming rate with 1-20 ℃/min is heated to 600-1000 ℃, behind the insulation 0.5-10h, cools off with stove.
10. a lithium ion battery is used negative plate, it is characterized in that: comprise substrate, and be coated in the arbitrary described silicon-carbon composite cathode material of suprabasil claim 1 to 9.
11. lithium ion battery; Comprise battery container, electrode group and electrolyte; Electrode group and electrolyte are sealed in the battery container, and the electrode group comprises positive pole, barrier film and negative pole, it is characterized in that: said negative pole is that the described lithium ion battery of claim 10 is used negative plate.
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