CN105261733B - The preparation method of nano silicon-based/carbon composite - Google Patents
The preparation method of nano silicon-based/carbon composite Download PDFInfo
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- CN105261733B CN105261733B CN201510566512.9A CN201510566512A CN105261733B CN 105261733 B CN105261733 B CN 105261733B CN 201510566512 A CN201510566512 A CN 201510566512A CN 105261733 B CN105261733 B CN 105261733B
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a kind of preparation method of nano silicon-based/carbon composite, coats microporous carbonaceous layer first in nanometer silicon face in liquid phase using organic resin and pore creating material first, and then using fermentation starch as carbon source, coated, high temperature cabonization preparation.Using the inventive method can be prepared architectural feature in " pomegranate " type it is nano silicon-based/carbon composite, when applied to lithium ion battery negative material is made, can effectively solve volume in process of intercalation drastically to expand and Particle Breakage, efflorescence in cyclic process, the problem of coming off, the specific capacity of material is up to 450 950mAh/g, cycle charge-discharge after 500 weeks capability retention be 85~92%.
Description
Technical field
The present invention relates to a kind of preparation method of nano silicon material, more particularly to a kind of nano silicon-based/carbon composite
Preparation method.
Background technology
The theoretical specific capacity of the graphite-like carbon negative pole material of now widely used lithium ion battery is only 372mAh/g, limit
Application of the lithium ion battery to high-energy-density direction is made.Silica-base material is due to its high embedding lithium capacity, high-lithium ion diffusion energy
Power, have become the first choice of lithium ion battery negative material carbon alternative materials.But because Si is during Electrochemical lithiation,
Complicated phase transformation adjoint great Volume Changes simultaneously occur, more than 300% volume is up to during the embedding de- lithium of silica-base material
Change, it is ruptured in charge and discharge process, efflorescence, come off, cause cycle performance of battery drastically to decline.To overcome these to lack
Fall into, it is by coating the method for one layer of carbon in Si particle surfaces come the elimination Si of part in embedding de- lithium process to study at present more
In Volume Changes.This method is only capable of being lifted the cycle performance of material to a certain extent, it is impossible to really solves active matter
Matter breakage of particles, efflorescence, the problem of gradually being come off from collector.Nano material can effectively suppress breakage of particles, efflorescence, lifting
Cycle performance.Research shows, when silicon nano particle diameter reaches 10nm, is circulated even across long-time, particle will not also be broken
Split, efflorescence.However, at present commercialization nano silica fume average grain diameter substantially all in more than 50nm, therefore still occur rupture, efflorescence it
Phenomenon.
The content of the invention
The present invention is intended to provide a kind of preparation method of nano silicon-based/carbon composite, silicon substrate/carbon composite of preparation
When for lithium ion battery negative material, the volume avoided in process of intercalation drastically expands, so as in circulating battery process
In occur without Particle Breakage, efflorescence, come off.The present invention is realized by following scheme：
A kind of preparation method of nano silicon-based/carbon composite, comprises the following steps：
(I) preparation of carbon-coated nano silicon：After organic resin is dissolved in into organic solvent, by resin and organic pore-forming agents mole
Than for 1:The ratio of (0.1~1), the pore creating material for dissolving in organic solvent is added thereto, after pore creating material dissolving, by organic tree
The mass ratio of fat and silicon is 1:The ratio of (10~1) adds nano silica fume thereto again, is done again through vacuum after ultrasonic disperse
Dry --- high temperature cabonization under the conditions of protective atmosphere --- crushes, and high temperature cabonization can prepare graphitic carbon negative electrode material side using existing
High temperature cabonization technique in method.The band micropore using nano Si as one layer of about 10~50 nanometer thickness of core Surface coating has been made in the step
Hard carbon layer, in the carbon-coated nano silicon of " pomegranate seed " feature.
(II) preparation of silicon-carbon compound precursor thing：After starch dispersion is formed into suspension in water, dried yeast powder is added,
It is afterwards 1 by the mass ratio of starch and composite particles:The ratio of (0.1~1), added into starch suspension made from the Ith step
The composite particles of nano-silicon coated with carbon bed, it is dispersed with stirring after 5~10 DEG C of vacuum drying.
(III) predecessor is carbonized：By silicon-carbon compound precursor thing made from the IIth step after certain time is stored at room temperature, then at
Room temperature~100 DEG C are heated, after being incubated 5-10 hours, 800~1200 DEG C of progress high temperature cabonizations in protective atmosphere.After carbonization
The silicon-carbon composite cathode material particle in " pomegranate type " architectural feature is made through crushing in material.
The preferred phenolic resin of organic resin or and Petropols in the Ith step.The preferred naphthalene of pore creating material, menthol or
Borneol.
Experiment is found, is 1 by the mass ratio of starch and dried yeast powder in the IIth step:(0.01~0.05) add
Dried yeast powder, material property is more preferably.
In order to reduce specific surface area and enhancing through the conduction between nano silicon-based/carbon composite particle made from the IIIth step
Ability, after the IIIth step, using the technique of existing liquid phase coating graphite, in the table of nano silicon-based/carbon composite
Bread covers pitch or glucose, after again through vacuum or spray drying --- high temperature cabonization.
Compared with the prior art, advantages of the present invention is embodied in：
1. the architectural feature that nano silicon-based/carbon composite particle is in " pomegranate " type is made using the method for the present invention,
During applied to making lithium ion battery negative material, can effectively solve volume in process of intercalation and drastically expanding and in cyclic process
Grain is broken, efflorescence, and the problem of coming off, the specific capacity of material is up to 450-950mAh/g, cycle charge-discharge capacity holding after 500 weeks
Rate is 85~92%.
2. in the preparation technology of the present invention, the characteristic of micropore can be produced using amylofermentation, by the carbon of " pomegranate seed " feature
Cladding nano-silicon is scattered in the carbon base body with micropore, further provides cushion space for the release of silicon swelling stress, while can
The penetrating power and electronics conduction velocity of electrolyte are improved, so as to improve the cyclical stability of electrode material.
Embodiment
Embodiment 1
A kind of preparation method of nano silicon-based/carbon composite, is prepared according to the following steps：
The preparation of (I) step carbon-coated nano silicon：After phenolic resin is dissolved in into absolute ethyl alcohol, by resin and organic pore-forming agents
The mol ratio of naphthalene is 1:1 ratio, adds naphthalene thereto, is 1 by the mass ratio of phenolic resin and silicon after naphthalene dissolving:10
Ratio, the nano silica fume that particle diameter D50 is 50nm is added thereto, ultrasonic disperse 60min is dried in vacuo after 200 DEG C, blanket of nitrogen
Under the conditions of, with 10 DEG C/min to 800 DEG C of insulation 360min of heating rate, room temperature is naturally cooled to, then crush；
The preparation of (II) step silicon-carbon compound precursor thing：Cornstarch is dispersed in water after forming suspension, by shallow lake
The mass ratio of powder and dried yeast powder is 1:0.05 adds dried yeast powder, is afterwards 1 by the mass ratio of starch and composite particles:1
Ratio, the composite particles of nano-silicon coated with carbon bed made from the Ith step are added into starch suspension, stir 120min, will
Particle disperses, then at 5 DEG C of vacuum drying；
(III) step predecessor is carbonized：Silicon-carbon compound precursor thing made from IIth step is stood into 300min in 30 DEG C, then at
After 90 DEG C of heating, 1200 DEG C of progress high temperature cabonizations, carbonization time 360min in blanket of nitrogen.Material after carbonization is through powder
It is broken, the silicon-carbon composite cathode material particle in " pomegranate type " architectural feature is made, the Task-size Controlling of particle is at 3~5 μm.
(IV) step liquid phase is coated on after the IIIth step again, in the surface liquid phase of nano silicon-based/carbon composite
Method coat pitch, after again through vacuum or spray drying --- high temperature cabonization.Obtain nano silicon-based/carbon composite.
Obtained nano silicon-based/carbon composite is used for negative electrode of lithium ion battery, and specific capacity is about 950mAh/g, and circulation is filled
Capability retention is 85~92% after discharging 500 weeks；Contrastingly, using elementary silicon as lithium-ion negative pole, although specific capacity
1200mAh/g, but in 500 weeks circulation volume conservation rates 23%；Using existing nucleocapsid structure Si-C composite material as negative
Pole, specific capacity 550mAh/g, 500 weeks circulation volume conservation rates 72%.Material prepared by the inventive method was in specific capacity and 500 weeks
The combination property of circulation volume conservation rate is more excellent.
Obtained nano silicon-based/carbon composite is fabricated to negative electrode of lithium ion battery as stated above, and battery passes through 100 weeks
After charge and discharge cycles, electrode slice surface topography is observed using scanning electron microscope sem, the results showed that substantially splitting does not occur in electrode surface
Line, powder of detached phenomenon.
Embodiment 2
Method and steps substantially the same manner as Example 1, but have following difference：
1. in the Ith step, the mol ratio of resin and organic pore-forming agents naphthalene is 1:0.1, the mass ratio of phenolic resin and silicon is
1:1 ratio, the particle diameter D50 of nano silica fume is 10nm, and ultrasonic disperse 60min is dried in vacuo after 200 DEG C, blanket of nitrogen condition
Under, with heating rate, 10 DEG C/min to 800 DEG C is incubated 10 hours.
2. the mass ratio of starch and dried yeast powder is 1 in the IIth step:0.01, the mass ratio of starch and composite particles is 1:
0.1。
3. the IVth step is not needed.
Claims (6)
- A kind of 1. preparation method of nano silicon-based/carbon composite, it is characterised in that：Comprise the following steps,(I) preparation of carbon-coated nano silicon：After organic resin is dissolved in into organic solvent, it is by resin and organic pore-forming agents mol ratio 1:The ratio of (0.1~1), add dissolve in the pore creating material of organic solvent thereto, after pore creating material dissolving, by organic resin with The mass ratio of silicon is 1:The ratio of (10~1) adds nano silica fume thereto again, vacuum dried again after ultrasonic disperse --- protect The high temperature cabonization protected under atmospheric condition --- crush；(II) preparation of silicon-carbon compound precursor thing：After starch dispersion is formed into suspension in water, dried yeast powder is added, afterwards It is 1 by the mass ratio of starch and composite particles:The ratio of (0.1~1), nanometer made from the Ith step is added into starch suspension Silicon face coats the composite particles of carbon-coating, is dispersed with stirring, in 5~10 DEG C of vacuum drying；(III) predecessor is carbonized：By silicon-carbon compound precursor thing is after certain time is stored at room temperature made from the IIth step, then at room temperature ~100 DEG C but without heating under conditions of room temperature, after being incubated 5-10 hours, in protective atmosphere 800~1200 DEG C carry out it is high Temperature carbonization, is finally crushed.
- 2. the preparation method of nano silicon-based/carbon composite as claimed in claim 1, it is characterised in that：In the Ith step The preferred phenolic resin of organic resin or/and Petropols.
- 3. the preparation method of nano silicon-based/carbon composite as claimed in claim 1, it is characterised in that：In the Ith step The preferred naphthalene of pore creating material, menthol or borneol.
- 4. the preparation method of nano silicon-based/carbon composite as described in one of claims 1 to 3, it is characterised in that：Described It is 1 by the mass ratio of starch and dried yeast powder in IIth step:(0.01~0.05) dried yeast powder is added.
- 5. nano silicon-based/carbon composite preparation method as described in one of claims 1 to 3, it is characterised in that：Described After III step, after the surface of nano silicon-based/carbon composite is using liquid phase method cladding pitch or glucose again through vacuum or Spray drying --- high temperature cabonization.
- 6. nano silicon-based/carbon composite preparation method as claimed in claim 4, it is characterised in that：In the IIIth step Afterwards, it is dry through vacuum or spraying again after the surface of nano silicon-based/carbon composite is using liquid phase method cladding pitch or glucose It is dry --- high temperature cabonization.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE102016202458A1 (en) * | 2016-02-17 | 2017-08-17 | Wacker Chemie Ag | Process for producing Si / C composite particles |
| CN105633380A (en) * | 2016-03-04 | 2016-06-01 | 中国科学院新疆理化技术研究所 | Preparation method for starch-based porous hard carbon negative electrode material of lithium ion battery |
| CN107204431B (en) * | 2016-03-16 | 2020-02-21 | 比亚迪股份有限公司 | Lithium ion battery negative electrode active material, preparation method thereof, negative electrode containing negative electrode active material and battery |
| CN105932320A (en) * | 2016-05-18 | 2016-09-07 | 河南田园新能源科技有限公司 | Method for preparing composite cathode material by modification of graphite |
| CN106410164B (en) * | 2016-11-24 | 2019-02-12 | 盐城工学院 | A kind of anode material and its preparation method and application |
| CN106784707B (en) * | 2016-12-28 | 2019-06-04 | 江西正拓新能源科技股份有限公司 | A kind of preparation method of nano-silicon-carbon composition lithium ion battery cathode material |
| CN107170962A (en) * | 2017-04-17 | 2017-09-15 | 厦门高容新能源科技有限公司 | A kind of lithium ion battery silicium cathode electrode slice and preparation method thereof |
| CN106898756B (en) * | 2017-04-24 | 2020-02-14 | 广东烛光新能源科技有限公司 | Silicon-carbon negative electrode material and preparation method thereof |
| CN108565431B (en) * | 2018-04-24 | 2021-08-20 | 中国矿业大学 | Method for preparing silicon-carbon composite negative electrode material of lithium ion battery by taking konjac flour as carbon source |
| CN111540896A (en) * | 2020-05-07 | 2020-08-14 | 七台河万锂泰电材有限公司 | Preparation method of silicon-carbon composite negative electrode material |
| CN112736237B (en) * | 2021-01-19 | 2023-05-02 | 贵州大学 | Preparation method of green low-cost silicon-carbon anode material with three-dimensional porous structure |
| CN114142005B (en) * | 2021-11-09 | 2023-03-31 | 广东凯金新能源科技股份有限公司 | Long-circulation low-expansion inner hole structure silicon-carbon composite material, and preparation method and application thereof |
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| US10135062B2 (en) * | 2011-12-21 | 2018-11-20 | Nexeon Limited | Fabrication and use of carbon-coated silicon monoxide for lithium-ion batteries |
| CN103560233A (en) * | 2013-11-08 | 2014-02-05 | 湖南大学 | Carbon coated silicon graphite cathode material of lithium ion battery and preparation method thereof |
| CN104868107B (en) * | 2015-03-11 | 2019-01-18 | 北京壹金新能源科技有限公司 | A kind of lithium ion battery spherical Si-C composite material and its preparation method and application |
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Denomination of invention: Preparation method of nano silicon-based/carbon composite material Effective date of registration: 20190923 Granted publication date: 20171117 Pledgee: Jinzhou Branch of Hunan Ningxiang Rural Commercial Bank Co., Ltd. Pledgor: Hunan Branch Star graphite Co. Registration number: Y2019330000081 |
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Date of cancellation: 20201120 Granted publication date: 20171117 Pledgee: Jinzhou Branch of Hunan Ningxiang Rural Commercial Bank Co.,Ltd. Pledgor: HUNAN SHINZOOM TECHNOLOGY Co.,Ltd. Registration number: Y2019330000081 |