CN107528055A - A kind of porous silicon carbon material and preparation method for cathode of lithium battery - Google Patents
A kind of porous silicon carbon material and preparation method for cathode of lithium battery Download PDFInfo
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- CN107528055A CN107528055A CN201710747636.6A CN201710747636A CN107528055A CN 107528055 A CN107528055 A CN 107528055A CN 201710747636 A CN201710747636 A CN 201710747636A CN 107528055 A CN107528055 A CN 107528055A
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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
- H01M4/366—Composites as layered products
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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
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- 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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- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a kind of porous silicon carbon material and preparation method for cathode of lithium battery.The porous silicon carbon material is formed by two kinds of Material claddings of silicon and carbon, and silicone content is in 7 10wt%；Wherein silicon is in porous spherical particle, and carbon is graphite flake, and silicon is attached on graphite flake, and graphite flake is distributed in coated, the crisscross stacking of lamellar graphite piece, and piece overlaps with piece and forms a large amount of holes, and wherein silicon porous spherical particle diameter is between 100nm 500nm.The porous Si-C composite material is obtained present invention also offers the chemical gas-phase deposition process for preparing for preparing the porous silica material, and by the heat treatment of porous silicon powder and graphite flake at high temperature.When porous Si-C composite material is made as lithium cell cathode material in the present invention, battery energy density reaches 550 800mAh/g, and circulating battery reaches 400 times.
Description
Technical field
The present invention relates to a kind of field of lithium, more particularly to a kind of porous silicon carbon material and system for cathode of lithium battery
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.
But the lithium ion battery that carbon material is not met by future must be to the demand that high power capacity direction is developed, and it stores up lithium and held
Amount is high not enough, and the theoretical energy density for the carbon material graphite being most widely used at present is 372mAh/g, what it can accomplish
Power capacity density will realize that electrokinetic cell energy density reaches current industry 300wh/kg target in below 250wh/kg,
It may not realized using traditional graphite material.And the theoretical energy density of silicon materials is up to more than its 10 times
4200mAh/g, by adding silicon in the carbon materials such as graphite to lift battery energy density be the generally acknowledged direction of industry, silicon
Energy density can improve more than 200% after carbon is compound, can meet the capacity requirement of portable high power power supply, can also meet to mix
Closing the high power that electric automobile proposes to lithium ion battery needs.But a technical problem very intractable at present be present in it,
In embedding, the de- cyclic process of lithium, there is serious volumetric expansion and contraction in silicium cathode material, cause destruction and the machine of material structure
Tool efflorescence, so as to cause the decline of electrode cycle performance.Carbon silicon is compound, and carbon material can alleviate silicon violent volume in cyclic process
Change the phenomenon that the inner tensions brought cause electrode pad material efflorescence to be collapsed.
The content of the invention
The problem of present invention exists for the actual demand of lithium ion battery development and prior art, offer one kind is provided and is used for
The porous silicon carbon material and preparation method of cathode of lithium battery.
The invention provides a kind of porous silicon carbon material for cathode of lithium battery, described porous silicon carbon material by silicon and
Two kinds of Material claddings of carbon form, and silicone content is in 7-10wt%；Wherein silicon is in porous spherical particle, and carbon is graphite flake, and silicon is attached to
On graphite flake, and graphite flake is distributed in coated, the crisscross stacking of lamellar graphite piece, and piece overlaps with piece and forms a large amount of holes,
Wherein silicon porous spherical particle diameter is between 100nm-500nm.
Present invention also offers the preparation method for preparing above-mentioned porous silicon carbon material, comprise the following steps that：
(1) chemical gaseous phase depositing process is used, with SiH4For presoma, it is passed into vacuum-tight horizontal pipe furnace；
CO is passed through in horizontal pipe furnace2, SiH4With CO2Flow-rate ratio be 1:1-1:2；1-2 hours are reacted at a temperature of 1200 DEG C,
Reaction pressure 10-30Pa；Then room temperature is naturally cooled to, obtains the spherical nano-silicon powder containing a large amount of holes；
(2) porous silicon powder is mixed according to mass ratio 1 with graphite flake:5-1:7 are dissolved in ethanol, and magnetic agitation 30min,
Form suspension；It is placed in 80 DEG C of vacuum drying box 12 hours；It is then placed in tube furnace, in argon gas atmosphere, at 780-850 DEG C
Heat treatment 4 hours, then natural cooling, obtains porous Si-C composite material.
The beneficial effects of the present invention are：When porous Si-C composite material is made as lithium cell cathode material in the present invention,
Battery energy density reaches 550-800mAh/g, and circulating battery reaches 400 times.Illustrate the addition of silicon materials, effectively improve
Battery energy density, simultaneously because carbon material and silicon is compound, alleviate what silicon violent Volume Changes in cyclic process were brought
Inner tensions cause the destruction of material structure and the decline of electrode cycle performance caused by.
Brief description of the drawings
Fig. 1 is that the SEM of porous Si-C composite material made from embodiment 1 schemes.
Fig. 2 is embodiment 1 when porous Si-C composite material is made is lithium cell cathode material, close in 300mA/g electric current
Charging and discharging curve under degree.
Embodiment
The present invention is further illustrated below in conjunction with drawings and the specific embodiments.
Embodiment 1
(1) chemical gaseous phase depositing process is used, with SiH4For presoma, it is passed into vacuum-tight horizontal pipe furnace；
CO is passed through in horizontal pipe furnace2, SiH4With CO2Flow-rate ratio be 1:1；Reacted 1 hour at a temperature of 1200 DEG C, reaction pressure
Strong 10Pa；Then room temperature is naturally cooled to, obtains the spherical nano-silicon powder containing a large amount of holes；
(2) porous silicon powder is mixed according to mass ratio 1 with graphite flake:5 are dissolved in ethanol, and magnetic agitation 30min, are formed
Suspension；It is placed in 80 DEG C of vacuum drying box 12 hours；It is then placed in tube furnace, 4 is heat-treated in argon gas atmosphere, at 780 DEG C
Hour, then natural cooling, obtains porous Si-C composite material.
Embodiment 2
(1) chemical gaseous phase depositing process is used, with SiH4For presoma, it is passed into vacuum-tight horizontal pipe furnace；
CO is passed through in horizontal pipe furnace2, SiH4With CO2Flow-rate ratio be 1:1.5；React 1.5 hours at a temperature of 1200 DEG C, instead
Answer pressure 20Pa；Then room temperature is naturally cooled to, obtains the spherical nano-silicon powder containing a large amount of holes；
(2) porous silicon powder is mixed according to mass ratio 1 with graphite flake:6 are dissolved in ethanol, and magnetic agitation 30min, are formed
Suspension；It is placed in 80 DEG C of vacuum drying box 12 hours；It is then placed in tube furnace, 4 is heat-treated in argon gas atmosphere, at 800 DEG C
Hour, then natural cooling, obtains porous Si-C composite material.
Embodiment 3
(1) chemical gaseous phase depositing process is used, with SiH4For presoma, it is passed into vacuum-tight horizontal pipe furnace；
CO is passed through in horizontal pipe furnace2, SiH4With CO2Flow-rate ratio be 1:2；Reacted 2 hours at a temperature of 1200 DEG C, reaction pressure
Strong 30Pa；Then room temperature is naturally cooled to, obtains the spherical nano-silicon powder containing a large amount of holes；
(2) porous silicon powder is mixed according to mass ratio 1 with graphite flake:7 are dissolved in ethanol, and magnetic agitation 30min, are formed
Suspension；It is placed in 80 DEG C of vacuum drying box 12 hours；It is then placed in tube furnace, 4 is heat-treated in argon gas atmosphere, at 850 DEG C
Hour, then natural cooling, obtains porous Si-C composite material.
Porous Si-C composite material made from embodiments above is observed by ESEM (SEM), as Fig. 1 is
The SEM figures of porous Si-C composite material made from embodiment 1, from the figure, it can be seen that porous spherical silica flour is attached to graphite flake
On, and graphite flake is distributed in coated, the crisscross stacking of lamellar graphite piece, and a large amount of holes are formed between piece and piece, spherical silica flour
Diameter is between 100nm-500nm.And the composition of the porous Si-C composite material of each embodiment is tested by XRD, silicone content exists
7-10wt%.
By porous Si-C composite material made from each embodiment and active material and PVDF according to mass ratio 1：8：1 is carried out
Mixing, grinding, NMP processing procedure slurries are then added, are applied on nickel foam pole piece, and dried at 70-80 DEG C, tabletting afterwards；
Button cell is made using lithium metal as to electrode.Discharge and recharge and loop test are carried out afterwards, if Fig. 2 is that embodiment 1 is made porous
When Si-C composite material is lithium cell cathode material, the charging and discharging curve under 300mA/g current density.Test result is shown
Battery energy density is in 550-800mAh/g, and when battery capacity decays to the 80% of rated capacity, the circulating battery undergone is secondary
Number reaches 400 times；Such as the specific data that following table one is each embodiment electrical performance testing.
Each embodiment electrical performance testing data of table one
Obviously, embodiments described above is only part of the embodiment of the present invention, rather than whole embodiments.Base
Embodiment in the present invention, those of ordinary skill in the art obtained under the premise of creative work is not made it is all its
His embodiment, belongs to the scope of protection of the invention.
Claims (3)
- A kind of 1. porous silicon carbon material and preparation method for cathode of lithium battery, it is characterised in that：The porous silicon carbon material Formed by two kinds of Material claddings of silicon and carbon, the silicon is graphite flake in porous spherical particle shape, carbon, and the silicon is attached to graphite On piece, and graphite flake is distributed in coated；The crisscross stacking of lamellar graphite piece, and piece overlaps with piece and forms a large amount of holes.
- 2. a kind of porous silicon carbon material and preparation method for cathode of lithium battery according to claim 1, its feature exist In：Silicon porous spherical particle diameter is between 100nm-500nm, and silicone content is in 7-10wt% in the porous silicon carbon material.
- 3. a kind of porous silicon carbon material and preparation method for cathode of lithium battery according to claim 1 or 2, its feature It is to include step as follows：1) chemical gaseous phase depositing process is used, with SiH4For presoma, it is passed into vacuum-tight horizontal pipe furnace；In level CO is passed through in tube furnace2, SiH4With CO2Flow-rate ratio be 1:1-1:2；1-2 hours, reaction pressure are reacted at a temperature of 1200 DEG C Strong 10-30Pa；Then room temperature is naturally cooled to, obtains the spherical nano-silicon powder containing a large amount of holes；2) porous silicon powder is mixed according to mass ratio 1 with graphite flake:5-1:7 are dissolved in ethanol, and magnetic agitation 30min, are formed Suspension；It is placed in 80 DEG C of vacuum drying box 12 hours；It is then placed in tube furnace, in argon gas atmosphere, at 780-850 DEG C at heat Reason 4 hours, then natural cooling, obtains porous Si-C composite material.
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Citations (6)
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| 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 |
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| CN103904307A (en) * | 2012-12-24 | 2014-07-02 | 宁波杉杉新材料科技有限公司 | Silicon-carbon composite material, preparation method and application thereof |
| CN104577084A (en) * | 2015-01-20 | 2015-04-29 | 深圳市贝特瑞新能源材料股份有限公司 | Nano silicon composite negative electrode material for lithium ion battery, preparation method and lithium ion battery |
| CN106784743A (en) * | 2017-02-28 | 2017-05-31 | 山东泰纳新材料科技有限公司 | A kind of low thermal expansion porous silicon/graphite combination electrode material and preparation method thereof |
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- 2017-08-25 CN CN201710747636.6A patent/CN107528055A/en not_active Withdrawn
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| CN104577084A (en) * | 2015-01-20 | 2015-04-29 | 深圳市贝特瑞新能源材料股份有限公司 | Nano silicon composite negative electrode material for lithium ion battery, preparation method and lithium ion battery |
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