CN107492649A - A kind of silicon carbon material for cathode of lithium battery and preparation method thereof - Google Patents
A kind of silicon carbon material for cathode of lithium battery and preparation method thereof Download PDFInfo
- Publication number
- CN107492649A CN107492649A CN201710747580.4A CN201710747580A CN107492649A CN 107492649 A CN107492649 A CN 107492649A CN 201710747580 A CN201710747580 A CN 201710747580A CN 107492649 A CN107492649 A CN 107492649A
- Authority
- CN
- China
- Prior art keywords
- silicon
- cnt
- carbon material
- preparation
- cathode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- H01M4/366—Composites as layered products
-
- 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
-
- 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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 discloses a kind of silicon carbon material for cathode of lithium battery and preparation method thereof, and the silicon carbon material is by two kinds of Material claddings of silicon and CNT；Wherein CNT is distributed in shrub plexi, and a diameter of 100 150nm of CNT, nano silicon particles are closely adhered on CNT outer wall, forms coated to CNT, and a large amount of holes are formed on surface.The invention also discloses a kind of preparation method of the silicon carbon material：Silicon-dioxide powdery is with multi-walled carbon nanotube according to mol ratio 1：14 20, carry out being fully ground mixing, be dissolved in absolute ethyl alcohol, stirring is sufficiently mixed it；Zinc powder body is added, normal temperature ultrasonic agitation 30min, forms suspension；Then 80 DEG C of vacuum drying box 12 hours is placed on again forms block；It is then placed in tube furnace, is heat-treated 23 hours at 650 800 DEG C under closed vacuum environment, then natural cooling；Obtain Si-C composite material.The material has high energy density and good cyclical stability.
Description
Technical field
The present invention relates to a kind of field of lithium, more particularly to a kind of Si-C composite material for cathode of lithium battery and its
Preparation method.
Background technology
Lithium ion battery with energy density it is high, have extended cycle life and be environmentally friendly the advantages that progressively substitute ni-mh electricity
Pond, turn into most promising energy storage device.Particularly in recent years, with new-energy automobile, the height of portable type electronic product
Speed development, lithium ion battery have obtained wider concern and more in-depth study.
Negative material is the key components of lithium ion battery, and it directly affects the energy density of battery, circulation longevity
Key index, following lithium ion battery negative material such as life and security performance must develop to high power capacity direction, could solve
The problem of existing battery energy density is low.
Carbon material is the material that negative electrode of lithium ion battery is most widely used at present, it not only technique for applying technology maturation,
Capacity is higher, but also with excellent cycle performance, higher coulombic efficiency and stable discharge voltage plateau, with solvent phase
Capacitive is good, and high and stable operating voltage, preferable high temperature performance and security performance can be provided for lithium battery.Application at present is most
Theoretical energy density for extensive carbon material graphite is 372mAh/g, and the power capacity density that it can accomplish is in 250wh/kg
Below.
Lithium ion battery just develops towards high-energy-density direction, finally supporting for electric automobile, and really turns into industry and answer
The green sustainable energy that non-fossil generates electricity, therefore it is required that material has high reversible capacity.
The interlamellar spacing of CNT is slightly larger than the interlamellar spacing of graphite, and charge/discharge capacity is more than graphite, and CNT
Tubular structure will not collapse after the circulation of multiple charge-discharge, and cyclicity is good.Alkali metal such as lithium ion and CNT have strong phase
Interaction.The discharge capacity first that the lithium battery that negative material is made is made of CNT is up to 1600mAh/g, and reversible capacity is
700mAh/g, much larger than the theoretical reversible capacity 372mAh/g of graphite.And the theoretical energy density of silicon materials exceedes 10 times of graphite,
Up to 4200mAh/g, its energy density can meet the capacity requirement of portable high power power supply, can also meet hybrid electrically vapour
The high power that car proposes to lithium ion battery needs.But there is a technical problem very intractable at present in it, in the embedding, de- of lithium
In cyclic process, there is serious volumetric expansion and contraction in silicium cathode material, cause the destruction of material structure and mechanical efflorescence, from
And cause the decline of electrode cycle performance.Carbon silicon is compound, and carbon material can alleviate silicon violent Volume Changes in cyclic process and bring
Inner tensions cause the phenomenon that electrode pad material efflorescence is collapsed.
The content of the invention
The problem of present invention exists for the actual demand of lithium ion battery development and prior art, intend providing a kind of silicon-carbon
Composite and preparation method thereof.
The invention provides a kind of silicon carbon material for cathode of lithium battery and preparation method thereof is prepared, specific steps are such as
Under：
Silicon-dioxide powdery is with multi-walled carbon nanotube (MWCNT) according to mol ratio 1：14-20, carry out being fully ground mixing,
It is dissolved in absolute ethyl alcohol, stirring is sufficiently mixed it；Add and silicon dioxide powder body mass ratio 1.2：1 zinc powder body, normal temperature
30min is stirred by ultrasonic, forms suspension；Then 80 DEG C of vacuum drying box 12 hours is placed on again forms block；It is then placed in
In tube furnace, 2-3 hours are heat-treated at 650-800 DEG C under closed vacuum environment；The mixing of argon gas and hydrogen is passed through afterwards
Gas is protective atmosphere, and 0.5-1 hours are incubated at 350-400 DEG C；Then natural cooling.Obtain Si-C composite material.Wherein
When being passed through the mixed gas of argon gas and hydrogen, the volume ratio of argon gas and hydrogen is 10:1.
By above-mentioned steps, silica reacts with Mg at high temperature, is reduced into silicon powder particle, and answer with MWCNT
Close and form last obtained Si-C composite material, be the compound of two kinds of materials of silicon and CNT, wherein silicone content is in 15-
20wt%；Wherein CNT is distributed in shrub plexi, and a diameter of 100-150nm of CNT, nano silicon particles are closely
It is attached on CNT outer wall, coated is formed to CNT, and a large amount of holes are formed on surface.
The beneficial effects of the present invention are：Using the addition of silicon, the energy density of composite is improved；Meanwhile pass through silicon
Compound with carbon, can alleviate the silicon inner tensions that violent Volume Changes are brought in cyclic process causes electrode pad material efflorescence
The phenomenon to collapse, and using the tubular morphology feature of CNT, can further avoid in cyclic process because silicon is acute
The inner tensions that strong Volume Changes are brought cause the destruction of material structure and the decline problem of electrode cycle performance, and adding makes
With the cyclical stability of the lithium ion battery of the obtained Si-C composite material.And obtained Si-C composite material is formed on surface
Coarse loose structure, be two kinds of nanostructureds the multilevel hierarchy being compounded to form, new interface caused by it and larger
Transmission channel of specific surface area when adding it as lithium ion battery negative material, so as to lift the Si-C composite material
The electrology characteristic such as battery energy density.When the obtained Si-C composite material of the present invention is as lithium cell cathode material, the energy content of battery
Density reaches 1700-2000mAh/g, and circulating battery reaches 500 times.
Brief description of the drawings
Fig. 1 is that the SEM of Si-C composite material made from embodiment 1 schemes.
Fig. 2 be embodiment 1 made from Si-C composite material when being lithium cell cathode material, in 300mA/g current density
Under charging and discharging curve.
Embodiment
The present invention is further illustrated below in conjunction with drawings and the specific embodiments.
Embodiment 1
Silicon-dioxide powdery is with multi-walled carbon nanotube (MWCNT) according to mol ratio 1：14, carry out being fully ground mixing, be dissolved in
In absolute ethyl alcohol, stirring is sufficiently mixed it；Add and silicon dioxide powder body mass ratio 1.2：1 zinc powder body, normal temperature ultrasound
30min is stirred, forms suspension；Then 80 DEG C of vacuum drying box 12 hours is placed on again forms block；It is then placed in tubular type
In stove, it is heat-treated 3 hours at 650 DEG C under closed vacuum environment, the mixed gas for being passed through argon gas and hydrogen afterwards is protection
Atmosphere, 1 hour is incubated at 350 DEG C, the volume ratio of argon gas and hydrogen is 10:1；Then natural cooling, silicon-carbon composite wood is obtained
Material.
Embodiment 2
Silicon-dioxide powdery is with multi-walled carbon nanotube (MWCNT) according to mol ratio 1：20, carry out being fully ground mixing, be dissolved in
In absolute ethyl alcohol, stirring is sufficiently mixed it；Add and silicon dioxide powder body mass ratio 1.2：1 zinc powder body, normal temperature ultrasound
30min is stirred, forms suspension；Then 80 DEG C of vacuum drying box 12 hours is placed on again forms block；It is then placed in tubular type
In stove, it is heat-treated 2 hours at 800 DEG C under closed vacuum environment；The mixed gas for being passed through argon gas and hydrogen afterwards is protection
Atmosphere, 0.7 hour is incubated at 370 DEG C, the volume ratio of argon gas and hydrogen is 10:1；Then natural cooling, it is compound to obtain silicon-carbon
Material.
Embodiment 3
Silicon-dioxide powdery is with multi-walled carbon nanotube (MWCNT) according to mol ratio 1：18, carry out being fully ground mixing, be dissolved in
In absolute ethyl alcohol, stirring is sufficiently mixed it；Add and silicon dioxide powder body mass ratio 1.2：1 zinc powder body, normal temperature ultrasound
30min is stirred, forms suspension；Then 80 DEG C of vacuum drying box 12 hours is placed on again forms block；It is then placed in tubular type
In stove, it is heat-treated 3 hours at 750 DEG C under closed vacuum environment；The mixed gas for being passed through argon gas and hydrogen afterwards is protection
Atmosphere, 1 hour is incubated at 400 DEG C, the volume ratio of argon gas and hydrogen is 10:1；Then natural cooling, silicon-carbon composite wood is obtained
Material.
Porous Si-C composite material made from embodiments above is observed by ESEM (SEM), as Fig. 1 is
The SEM figures of Si-C composite material made from embodiment 1, from the figure, it can be seen that CNT is distributed in shrub plexi, carbon nanometer
A diameter of 100-150nm of pipe, nano silicon particles are closely adhered on CNT outer wall, and CNT is formed and coated
Shape, and a large amount of holes are formed on surface.And the composition of the Si-C composite material of each embodiment is tested by XRD, silicone content is in 15-
20wt%, specifically it is shown in Table the data of each embodiment test in one.
By Si-C composite material made from each embodiment and active material and PVDF according to mass ratio 1：8：1 is mixed
Close, grinding, then add NMP processing procedure slurries, be applied on nickel foam pole piece, and dried at 70-80 DEG C, tabletting afterwards；With
Lithium metal is that button cell is made to electrode.Discharge and recharge and loop test are carried out afterwards, are answered as silicon-carbon is made for embodiment 1 in Fig. 2
When condensation material is lithium cell cathode material, the charging and discharging curve under 300mA/g current density.Test result shows battery energy
Metric density is in 1700-2000mAh/g；When battery capacity decays to the 80% of rated capacity, the circulating battery number undergone reaches
To 500 times.Such as the specific data that following table one is each embodiment electrical performance testing.
Each embodiment test data of table one
Obviously, although present disclosure has been made complete and clearly described with regard to its disclosed embodiment,
It is not limited only to this, and embodiments described above is only part of the embodiment of the present invention, rather than whole embodiments.It is right
For the personnel of art, obtained institute is made improvements and substitutes to the present invention by the guidance of these statements
There is other embodiment, among the present invention.
Claims (5)
- A kind of 1. silicon carbon material for cathode of lithium battery and preparation method thereof, it is characterised in that：The silicon carbon material by silicon and Two kinds of Material claddings of CNT；Wherein CNT is distributed in shrub plexi, and nano silicon particles are closely adhered on carbon nanometer In pipe outer wall, coated is formed to CNT, and a large amount of holes are formed on surface.
- A kind of 2. silicon carbon material for cathode of lithium battery according to claim 1 and preparation method thereof, it is characterised in that： Silicone content is in 15-20wt%, a diameter of 100-150nm of CNT in the silicon carbon material.
- 3. a kind of silicon carbon material for cathode of lithium battery according to claim 1 or 2 and preparation method thereof, its feature exists In as follows including step：Silicon-dioxide powdery is with multi-walled carbon nanotube according to mol ratio 1：14-20, carry out being fully ground mixing, It is dissolved in absolute ethyl alcohol, stirring is sufficiently mixed it；Zinc powder body is added, normal temperature ultrasonic agitation 30min, forms suspension；So It is placed on 80 DEG C of vacuum drying box 12 hours again afterwards and forms block；It is then placed in tube furnace, under closed vacuum environment 2-3 hours are heat-treated at 650-800 DEG C；The mixed gas for being passed through argon gas and hydrogen afterwards is protective atmosphere, at 350-400 DEG C It is incubated 0.5-1 hours；Then natural cooling, Si-C composite material is obtained.
- A kind of 4. silicon carbon material for cathode of lithium battery according to claim 3 and preparation method thereof, it is characterised in that： The zinc powder body of addition is 1.2 with silicon dioxide powder body mass ratio：1.
- A kind of 5. silicon carbon material for cathode of lithium battery according to claim 3 and preparation method thereof, it is characterised in that： When being passed through the mixed gas of argon gas and hydrogen, the volume ratio of argon gas and hydrogen is 10:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710747580.4A CN107492649A (en) | 2017-08-25 | 2017-08-25 | A kind of silicon carbon material for cathode of lithium battery and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710747580.4A CN107492649A (en) | 2017-08-25 | 2017-08-25 | A kind of silicon carbon material for cathode of lithium battery and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107492649A true CN107492649A (en) | 2017-12-19 |
Family
ID=60645868
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710747580.4A Pending CN107492649A (en) | 2017-08-25 | 2017-08-25 | A kind of silicon carbon material for cathode of lithium battery and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107492649A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109659549A (en) * | 2019-01-14 | 2019-04-19 | 北京科技大学 | Lithium battery multilevel structure silicon-porous carbon compound cathode materials preparation method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102569756A (en) * | 2011-12-27 | 2012-07-11 | 上海交通大学 | Preparation method of silicon/graphene nanocomposite material for cathode of lithium ion battery |
| CN102983313A (en) * | 2012-12-05 | 2013-03-20 | 奇瑞汽车股份有限公司 | Silicon-carbon composite material and preparation method thereof, and lithium ion battery |
| CN105633374A (en) * | 2016-01-31 | 2016-06-01 | 湖南大学 | Preparation method of silicon-carbon-graphite composite anode material |
-
2017
- 2017-08-25 CN CN201710747580.4A patent/CN107492649A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102569756A (en) * | 2011-12-27 | 2012-07-11 | 上海交通大学 | Preparation method of silicon/graphene nanocomposite material for cathode of lithium ion battery |
| CN102983313A (en) * | 2012-12-05 | 2013-03-20 | 奇瑞汽车股份有限公司 | Silicon-carbon composite material and preparation method thereof, and lithium ion battery |
| CN105633374A (en) * | 2016-01-31 | 2016-06-01 | 湖南大学 | Preparation method of silicon-carbon-graphite composite anode material |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109659549A (en) * | 2019-01-14 | 2019-04-19 | 北京科技大学 | Lithium battery multilevel structure silicon-porous carbon compound cathode materials preparation method |
| CN109659549B (en) * | 2019-01-14 | 2021-02-12 | 北京科技大学 | Preparation method of multi-stage structure silicon-porous carbon composite negative electrode material for lithium battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103346324B (en) | Lithium ion battery cathode material and its preparation method | |
| CN108448080B (en) | Graphene-coated silicon/metal composite negative electrode material and preparation method thereof | |
| CN107994217B (en) | Preparation method of double-coated silicon-based composite material and lithium ion battery | |
| CN110620224A (en) | Negative electrode material for lithium battery, preparation method of negative electrode material and lithium battery | |
| CN104009210A (en) | Porous silicon/carbon composite material, and preparation method and application thereof | |
| CN109244377A (en) | A kind of preparation method of negative electrode of lithium ion battery Si-C composite material | |
| CN106099073A (en) | The preparation method of composite cathode material for lithium ion cell, composite cathode material for lithium ion cell and lithium ion battery | |
| CN105742695B (en) | A kind of lithium ion battery and preparation method thereof | |
| WO2022002057A1 (en) | Silicon-oxygen composite negative electrode material, negative electrode, lithium-ion battery, and preparation methods therefor | |
| CN112652758B (en) | Silicon oxide/carbon microsphere composite negative electrode material for lithium ion battery and preparation method thereof | |
| CN102867947A (en) | Method for preparing carbon/silicon composite anode material based on oligomeric silsesquioxane | |
| CN115714170B (en) | Preparation method of high-energy-density quick-charge anode material | |
| CN111193014A (en) | Cobaltosic oxide-nitrogen doped carbon/carbon nanocage composite material with eggshell-yolk structure and preparation method and application thereof | |
| CN106876684A (en) | A kind of lithium battery silicium cathode material, negative plate and the lithium battery prepared with it | |
| CN115207329A (en) | Preparation method of high-energy-density silicon carbon/mesocarbon microbead composite material | |
| CN107863498A (en) | A kind of preparation method of cathode material of lithium-ion power battery | |
| CN108807894B (en) | Polymer precursor converted Si/C lithium ion battery cathode material and preparation method thereof | |
| CN110534725B (en) | Silicon/carbon nano tube/carbon micron line and preparation method and application thereof | |
| CN102945950B (en) | Method for in-situ growth of carbon nanotube array on metal current collector | |
| CN117080407A (en) | Boron-doped composite silicon-based lithium ion battery anode material and preparation method thereof | |
| CN108878823B (en) | Preparation method of metal olivine coated nano silicon | |
| CN107492649A (en) | A kind of silicon carbon material for cathode of lithium battery and preparation method thereof | |
| CN108288705B (en) | Silicon-carbon negative electrode material for lithium ion battery and preparation method thereof | |
| CN112421002B (en) | High-capacity silicon-carbon material and preparation method thereof | |
| CN110739445B (en) | Preparation method of nitrogen-doped carbon/graphene/silicon self-supporting body composite electrode |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20171219 |
|
| WD01 | Invention patent application deemed withdrawn after publication |