CN106058207A - Silicon-carbon composite material, preparation method thereof and negative pole for lithium-ion battery - Google Patents
Silicon-carbon composite material, preparation method thereof and negative pole for lithium-ion battery Download PDFInfo
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- H—ELECTRICITY
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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- 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
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- 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
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- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a preparation method of a silicon-carbon composite material. The method is characterized by comprising the steps: introducing a gas mixture consisting of silicon tetrachloride gas and reducing carrier gas into a reaction chamber, in which a carbon material is placed, wherein the reducing carrier gas contains reductive gas; heating the gas mixture, so as to enable the reductive gas to reduce the silicon tetrachloride gas into elemental silicon and form the silicon-carbon composite material, in which the elemental silicon is deposited on the carbon material. The method has the advantages that the raw materials are cheap, the process is simple, and the product performance is excellent. The invention further provides the silicon-carbon composite material and a silicon-carbon composite material containing negative pole for a lithium-ion battery.
Description
Technical field
The present invention relates to Si-C composite material field, be specifically related to prepare the method for Si-C composite material, pass through the method
The Si-C composite material prepared and the negative pole for lithium ion battery comprising Si-C composite material.
Background technology
The improvement of electrode material is one of emphasis in the research and development of lithium ion battery.Silicon materials are as lithium ion battery
Negative pole has high theoretical capacity (～4200mAh/g) and low discharge potential (＜ 0.5V, Vs.Li/Li+) it is considered to be generation
Important candidate material for conventional graphite negative pole.
But silicon materials change in volume in charge and discharge process is relatively big (～300%), this is not only bad at circulating battery
During form stable SEI film, and the efflorescence of electrode material can also be caused, thus cause battery table to reveal quick capacity
Decay.
Silicon is combined with material with carbon element, can not only effectively alleviate electrode material volumetric expansion problem but also can be effective
Improve the electric conductivity of electrode material, promote the chemical property of composite.
In order to prepare Si-C composite material, distinct methods is attempted and is used.One class Si-C composite material is by carbonaceous
The siliceous material of material matrix and cover it is constituted.At present, when preparing this type of Si-C composite material, silane is generally used
Deng organosilicon as silicon source, expensive, and carbonaceous material generally uses the material such as CNT, carbon fiber, relatively costly.
For the method obtaining the Si-C composite material possessing good electrode material performance in the way of more cheap, still deposit
At needs.
Summary of the invention
In order to solve the problems referred to above, the invention provides techniques below scheme.
[1] a kind of method preparing Si-C composite material, it is characterised in that described method includes:
The mixed gas being made up of Silicon chloride. gas and reduction carrier gas is passed through the reative cell being wherein placed with material with carbon element
In, wherein said reduction carrier gas comprises reducibility gas；
Heat described mixed gas so that described Silicon chloride. gas reduction is elemental silicon by described reducibility gas, and
And form wherein said elemental silicon deposition Si-C composite material on the carbon material.
[2] according to the method described in [1], it is characterised in that the group of described reducibility gas choosing free the following composition:
Acetylene, hydrogen, methane, carbon monoxide, ammonia or combinations thereof.
[3] according to the method described in [1] or [2], it is characterised in that described reducibility gas is acetylene.
[4] according to [1] to the method according to any one of [3], it is characterised in that described material with carbon element is graphite or by right
Biological material carries out the biomass sources material with carbon element of pre-treatment acquisition.
[5] according to the method described in [4], it is characterised in that the group of described biological material choosing free the following composition:
Straw, rice husk, Folium Bambusae, corn cob or combinations thereof.
[6] according to the method described in [4], it is characterised in that described pre-treatment includes:
Described biological material is pulverized；
Described biological material is carried out acid boil；
Described biological material is carried out carbonization treatment；
With the biological material after hydrofluoric acid clean carbonization treatment, it is thus achieved that biomass sources material with carbon element.
[7] a kind of Si-C composite material prepared to the method according to any one of [6] according to [1].
[8] according to the Si-C composite material described in [7], it is characterised in that silicone content is in the range of 10-50 weight %.
[9] according to Si-C composite material described in [7] or [8], it is characterised in that described material with carbon element is graphite or by right
Biological material carries out the biomass sources material with carbon element of pre-treatment acquisition, and described biological material selects free the following composition
Group: straw, rice husk, Folium Bambusae, corn cob or combinations thereof.
[10] a kind of negative pole for lithium ion battery, described negative pole comprises according to [7] to the silicon according to any one of [9]
Carbon composite.
By technique scheme, a kind of method that the invention provides synthesis of carbon-silicon composite, required raw material valency
Lattice are cheap, materials safety, relatively low to equipment requirements, preparation flow environmental protection, and productivity is higher, and production cost is low, are beneficial to amplify production.
Present invention also offers a kind of carbon-silicon composite material, although its low production cost, but there is excellent performance.The present invention also carries
Having supplied to comprise the negative pole of this carbon-silicon composite material, it can meet the needs as lithium ion battery negative.
Accompanying drawing explanation
Fig. 1 is the X-ray diffractogram of the product that embodiment 1 obtains.
Fig. 2 is the scanning electron microscope (SEM) photograph of the product that embodiment 1 obtains.
Fig. 3 is the X-ray diffractogram of the product that embodiment 2 obtains.
Fig. 4 is Energy Dispersive X-ray (EDX) the detection distribution diagram of element of the product that embodiment 2 obtains.
Fig. 5 be the Si-C composite material that embodiment 2 obtains be charge and discharge cycles figure during 0.4A/g in electric current density.
Fig. 6 be the Si-C composite material that embodiment 2 obtains be charge and discharge cycles figure during 1.2A/g in electric current density.
Fig. 7 is the X-ray diffractogram of embodiment 4 products therefrom.
Fig. 8 is the scanning electron microscope (SEM) photograph of embodiment 4 products therefrom.
Fig. 9 be the Si-C composite material that embodiment 4 obtains be charge and discharge cycles figure during 0.4A/g in electric current density.
The Si-C composite material that obtains of Figure 10 embodiment 4 is charge and discharge cycles figure during 1.2A/g in electric current density.
Detailed description of the invention
A first aspect of the present invention provides a kind of method preparing Si-C composite material, it is characterised in that described method
Including: the mixed gas being made up of Silicon chloride. gas and reduction carrier gas is passed through and is wherein placed with in the reative cell of material with carbon element,
Wherein said reduction carrier gas comprises reducibility gas；Heat described mixed gas so that described reducibility gas is by described tetrachloro
SiClx gas reduction is elemental silicon, and forms wherein said elemental silicon deposition Si-C composite material on the carbon material.
Use Silicon chloride. as the source of silicon in Si-C composite material, with use organosilicon as compared with silicon source, raw material
Cheap and wide material sources, preparation flow environmental protection, productivity is higher, and production cost is low, is beneficial to amplify production.Especially it is possible to use
Industrial waste Silicon chloride., this had both reduced cost, had provided approach for recycling industrial waste again.
Reduction carrier gas in the mixed gas of the present invention is played and Silicon chloride. is loaded into reative cell and utilizes reduction therein
Silicon chloride. is reduced to property gas elemental silicon so that the effect of its vapour deposition.Reduction carrier gas as herein described only can be
By the blended gas of one or more reducibility gas species compositions.Reduction carrier gas can also be reducibility gas and noble gas
Blended gas, as long as this blended gas Silicon chloride. can be reduced to elemental silicon so that the effect of its vapour deposition i.e.
Can.Reducibility gas mentioned herein has the reproducibility for the silicon in Silicon chloride., i.e. reducibility gas can be in heating
Under the conditions of with react with Silicon chloride. generation gas phase, be zeroth order elemental silicon by the positive tetravalence Si reduction in Silicon chloride..Also publish originally
In gas, the existence of noble gas can be played regulation pressure, be improved the effects such as safety.The example of noble gas includes argon etc..
Preferably, the group of the described reducibility gas choosing free the following composition in reduction carrier gas: acetylene, hydrogen, methane, an oxidation
Carbon, ammonia or combinations thereof.Above-mentioned reducibility gas is easy to get and inexpensively, is greatly saved cost of material.It is highly preferred that reduction
Property gas is acetylene.Acetylene gas can react as reducibility gas under relatively low reduction temperature, and thermal cracking is produced simultaneously
Raw carbon co-deposits with the silicon of reduction, and the carbon herein co-deposited has important function for the stability promoting material.The most excellent
Selection of land, acetylene is 2: 1 with the mol ratio of Silicon chloride..
The heating of mixed gas of Silicon chloride. gas with reduction carrier gas only need to make reducibility gas can be with tetrachloro
SiClx gas reaction and by Si reduction therein.Reaction temperature can be 400 to 700 DEG C, preferably from about 550 DEG C.
The range of flow of mixed gas can be 1 to 100ml/min.Response time can be 0.5 to 24h, is preferably from about
6h。
Reative cell provides substantially closed space, as long as the silicon that its structure makes gas phase reaction generate can be deposited on
It is placed on material with carbon element therein.
As common for vapor deposition processes, can be by regulation temperature, gas flow rate, mixed gas group
The condition such as one-tenth, reative cell structure, material with carbon element placement location, is adjusted vapor deposition processes and product characteristics.The present invention's
Method can also include the step of purification, such as remove impurity (such as pickling, washing), filters, is dried.
Material with carbon element can be arbitrary material with carbon element.The method of the present invention can use cheap material with carbon element acquisition to possess excellent
The lithium ion battery negative Si-C composite material of performance, and prepare without using CNT, carbon fiber, Graphene etc. to be difficult to and
Expensive material with carbon element.
Preferably, the present invention can use graphite as material with carbon element.Graphite can be graphite ore, the most commercially available graphite
Ore deposit, have an advantage in that raw material be easy to get, with low cost.In the case of using graphite ore to be material with carbon element, the silicon-carbon that the present invention prepares
Composite still possesses good electrode property, may be used in lithium ion battery.
Preferably, described material with carbon element is the biomass sources material with carbon element by biological material carries out pre-treatment acquisition.By
The biomass sources material with carbon element that biological material obtains through the pre-treatment including carbonization has the natural knot being derived from biomass
Structure, function admirable when as lithium ion battery negative material.
It is highly preferred that described biological material select free the following form group: straw, rice husk, Folium Bambusae, corn cob,
Or combinations thereof.These materials are cheap and easy to get, in plentiful supply.
Same it is highly preferred that described pre-treatment includes: described biological material is pulverized；Described biological material is carried out
Acid is boiled；Described biological material is carried out carbonization treatment；With the biological material after hydrofluoric acid clean carbonization treatment, it is thus achieved that biological
Matter source material with carbon element.
The purpose that acid is boiled includes removing inorganic ion impurity.Boil it is, for example possible to use the hydrochloric acid of 4mol/L carries out acid.Acid
Boil and process needs heated by slurry, such as, can be heated to about 150 DEG C.
Carbonization treatment is to heat biological material under such as inert gas shieldings such as nitrogen, so that its carbonization.Carbon
The temperature that change processes can be between 300 to 900 DEG C.
The effect of hydrofluoric acid clean is to remove siliceous material therein such as silicon dioxide.For example, it is possible to 3mol/L hydrogen fluorine
Acid is cleaned and stirs 1-6h.
Between each step above, washing, the usual procedure such as dry can be comprised.
A second aspect of the present invention provides the Si-C composite material prepared by the method for first aspect.This silicon-carbon composite wood
The raw material of material is cheap, and preparation cost is low, and has excellent character, meets the needs as lithium ion battery negative.And,
The two kinds of elements compounding of Si-C composite material silicon-carbon so prepared are uniform.
Preferably, in described Si-C composite material, silicone content is in the range of 5-55 weight %, and more preferably 10-50 is heavy
Amount %, still more preferably 10 weight %.When silicon-carbon mass ratio is 1: 9, excellent material performance.
Preferably, the material with carbon element in described Si-C composite material is graphite or obtains by biological material is carried out pre-treatment
The biomass sources material with carbon element obtained, the group of described biological material choosing free the following composition: straw, rice husk, Folium Bambusae, Semen Maydis
Core or combinations thereof.Use graphite as the Si-C composite material low cost of material with carbon element and function admirable.Use biomass sources
Material with carbon element is as Si-C composite material low cost, and has the natural structure being derived from biomass, when bearing as lithium ion battery
The function admirable during material of pole.
A third aspect of the present invention provides the bearing for lithium ion battery of the Si-C composite material comprising second aspect
Pole.This negative pole is with low cost, but function admirable.This negative pole demonstrates the lithium storage content far above graphite cathode, its lithium storage content
372mAh/g close to 800mA h/g, relatively graphite negative electrodes improves about 2 times, and the circulation with high coulombic efficiency and length is steady
Qualitative, have extended cycle life.
Lithium ion battery height lithium storage content and long cyclical stability are by the structures shape of this material.Wherein invest
The silicon of carbon material surface is non-crystalline silicon, has preferable volumetric expansion mitigation, simultaneously because silicone content is relatively low, can effectively subtract
The fragmentation of few electrode material and the Volumetric expansion of reduction electrode material.Secondly, the main body of composite is material with carbon element,
Good conductivity, Volumetric expansion is few, can effectively promote the electric conductivity of electrode material, reduce the Volumetric expansion of material.
A kind of specific embodiments of the method for the present invention is as follows.
With Silicon chloride. for silicon source, utilize the reducibility gas of one-component or blending ingredients as carrier gas, by Silicon chloride.
It is loaded into reative cell to react, occurs redox reaction to obtain elemental silicon, and by vapour deposition, siliceous deposits is put in advance
Enter and through the carbon material surface of pre-treatment, thus prepare Si-C composite material.This gas phase deposition technology prepares silicon-carbon composite wood
Material, reaction raw materials is cheap and easy to get, and preparation process is simple, suitably controls reaction temperature, air flow rate and time, can effectively control
The generation of carborundum, can pass through Adjustment Tests parameter simultaneously, prepares the Si-C composite material of different silicone content.In vapour deposition
After process, it is not necessary to any subsequent treatment, it is advantageously implemented magnanimity and prepares Si-C composite material.
Raw material is as follows:
Silicon source, selected from Silicon chloride.；
Reproducibility carrier gas, selects acetylene gas, hydrogen, methane, carbon monoxide, ammonia or its corresponding combined hybrid gas.
Material with carbon element, selects biomass sources material with carbon element prepared by straw, rice husk, Folium Bambusae, corn cob or its mixing material, or choosing
Use graphite material.
Specifically comprise the following steps that
A) prepare biomass sources material with carbon element: shredded by the biological materials such as straw, through high temperature pickling, wash, dry, then
Process with high temperature cabonization, finally remove silicon dioxide by hydrofluoric acid clean, then obtain biomass sources material with carbon element through washing drying.Business
Product material with carbon element carries out 100 degrees Celsius of drying and processings.
B) above-mentioned material with carbon element is inserted in reactor, be passed through acetylene gas and Silicon chloride. gas in proportion, at acetylene
Heating 400 to 700 degrees Celsius with in Silicon chloride. atmosphere, keep 0.5～24h, reaction i.e. can get silicon-carbon after terminating multiple
Condensation material；
The Si-C composite material that the present invention obtains, element silicon is uniformly compounded in carbon material surface.
Preferably, described reducibility gas is acetylene gas；
Preferably, Silicon chloride. is 1: 2 with the mol ratio of acetylene gas；
Preferably, reaction temperature is 540-560 degree Celsius, such as from about 550 degrees Celsius；
Preferably, the response time is 4-8h, such as from about 6h；
Preferably, silicone content 5-50% in Si-C composite material, such as 10%.
Described reaction can be carried out in stainless steel reaction tube furnace.
Below in conjunction with embodiment, technical scheme is carried out clear, detailed description.It is understood that retouched
The embodiment stated is only the part of the present invention rather than whole embodiments.Based on the embodiment in the present invention, this area
The every other embodiment that obtained under not making creative work premise of technical work personnel.Broadly fall into the present invention's
Protection domain.
Embodiment 1: with Wheat Straw as raw material, prepares biomass sources material with carbon element
1) Wheat Straw material is pulverized, with the hydrochloric acid of 4mol/L, react 10h through 150 degrees Celsius, clear with deionized water
Wash three times and be dried.Then under the inert gas shieldings such as nitrogen, carry out 600 degrees Celsius of carbonization treatment, use 3mol/L Fluohydric acid. afterwards
Clean and stir 1-6h.It is dried to obtain Wheat Straw biomass sources material with carbon element through deionized water wash after.
2) use X light powder diffraction instrument (Philips X ' Pert Super diffract meter) to carry out X-ray diffraction to divide
Analysis, Fig. 1 is the X-ray diffraction spectrum of this embodiment gained powder body.As seen from the figure, in x-ray diffraction spectra 2 θ in the range of 10-80 degree
Not having the most sharp-pointed diffraction maximum, a steamed bread peak occur between 20 to 30 degree, representing this biomass sources material with carbon element is amorphous
State.
3) scanning electron microscope (SEM) photograph (Fig. 2) of product shows that this product is micron-sized structure, surfacing.
Embodiment 2: the biomass sources material with carbon element prepared with the Wheat Straw of embodiment 1, as substrate, utilizes vapour deposition to prepare
Si-C composite material.
1) the biomass sources material with carbon element of preparation is put in reative cell.By commercially available acetylene (mixed gas of acetylene and argon,
Volume ratio Ar: C2H2=9: 1) load Silicon chloride. (commercially available acetylene is 20: 1 with the volume ratio of Silicon chloride .) is passed through in reative cell,
Heating 550 degrees Celsius in the atmosphere containing acetylene and Silicon chloride., keep 8h, reaction prepares silicon-carbon after terminating multiple
Condensation material.
2) Fig. 3 is the X-ray diffraction spectrum of this embodiment gained powder body.Spectrogram shows that this powder body is amorphous phase, miscellaneous without other
Matter generates.
3) Fig. 4 is the Energy Dispersive X-ray detection distribution diagram of element of this embodiment gained powder body, and this figure shows that element silicon is equal
The even carbon material surface that is distributed in, silicon is 1: 9 with the element mass ratio of carbon.Analyzed by X-ray energy spectrum, measure silicon-carbon element quality
Ratio is also about 1: 9.
Embodiment 3: the Si-C composite material that embodiment 2 is obtained is applied to lithium ion battery negative material performance study
Product in above-described embodiment 2 is dressed up CR2016 button cell respectively, and (Shenzhen's roc Xiang transports to machinery science and technology to be had
Limit company), with lithium sheet for electrode, polyolefin porous membrane (Celgard 2500) is barrier film, with LiPF6Ethylene carbonate
(EC) and the mixed solution of dimethyl carbonate (DMC) (volume ratio 1: 1) is as electrolyte, CR2016 battery is at the hands of argon gas atmosphere
Casing completes.Silicon-carbon electrode uses the carboxylic first of the biomass Si-C composite material in the embodiment 2 of 60 weight %, 20 weight %
Base sodium cellulosate adhesive, the conductive black of 20%, water mix, and the substrate of electrode film is metal copper foil.In test temperature
It is under 25 degrees Celsius, to carry out electric performance test.Fig. 5-6 is the electrochemical lithium storage of the Si-C composite material of above-described embodiment 2 gained
Can figure.As it is shown in figure 5, reversible specific capacity is 800mA h/g after circulating 500 circles under the electric current density of 0.4A/g.Such as Fig. 6 institute
Showing, circulating 1000 circles under the electric current density of 1.2A/g, reversible specific capacity remains close to 600mA h/g.
Embodiment 4: with the kish pit wood material of commodity as substrate, utilize vapour deposition to prepare Si-C composite material.
1) commercial graphite pit wood material (commercially available from Yichang China Sciences Hengda Graphite Co., Ltd.) is put into reative cell
In.By commercially available acetylene (acetylene and the mixed gas of argon, volume ratio Ar: C2H2=9: 1) load Silicon chloride. (commercially available acetylene with
The volume ratio of Silicon chloride. is 20: 1) it is passed through in reative cell, the atmosphere containing acetylene and Silicon chloride. heats 550 and takes the photograph
Family name's degree, keeps 8h, reaction to prepare Si-C composite material after terminating.
2) Fig. 7 is the X-ray diffraction spectrum of this embodiment gained powder body.The diffraction maximum that spectrogram shows can index be six sides
The crystalline carbon material (JCPDS NO.26-1076) of phase, generates without other impurity.Having amorphous peak between 20～30 degree, explanation has
Non-crystalline material is deposited in crystalline carbon.
3) scanning electron microscope (SEM) photograph (Fig. 8) of product shows that this product is uniform micron-sized structure.
Embodiment 5: the Si-C composite material that embodiment 4 is obtained is applied to lithium ion battery negative material performance and grinds
Study carefully
As lithium ion battery negative material, the Si-C composite material in above-described embodiment 4 is carried out chemical property grind
Study carefully.This product is dressed up CR2016 button cell (Shenzhen Poxon Machinery Technology Co., Ltd.) respectively, and assembly method is such as
Described in embodiment 3.Silicon-carbon electrode uses the graphite silicon carbon composite in the embodiment 4 of 60 weight %, the carboxylic of 20 weight %
Sodium carboxymethylcellulose pyce adhesive, the conductive black of 20%, water mix, and the substrate of electrode film is metal copper foil.In test temperature
Degree is to carry out electric performance test under 25 degrees Celsius.Fig. 9-10 is the electrochemistry storage of the Si-C composite material of above-described embodiment 4 gained
Lithium performance map.As it is shown in figure 9, reversible specific capacity is close to 700mA h/g after circulating 300 circles under the electric current density of 0.4A/g.As
Shown in Figure 10, circulating 1000 circles under the electric current density of 1.2A/g, reversible specific capacity remains close to 500mA h/g.
Result shows, the present invention can be raw material through using cheap material with carbon element, Silicon chloride., through vapour deposition
Realize the preparation of Si-C composite material powder body.By controlling reducibility gas and Silicon chloride. ratio, reaction temperature, response time
Etc. factor, the material of the different silicon-carbon ratio of preparation.When this material is directly used in lithium ion battery negative material, demonstrate remote
Higher than the lithium storage content of graphite cathode with preferable cyclical stability, can bear as potential high performance lithium ion battery of future generation
Pole material.
Claims (10)
1. the method preparing Si-C composite material, it is characterised in that described method includes:
The mixed gas being made up of Silicon chloride. gas and reduction carrier gas is passed through and is wherein placed with in the reative cell of material with carbon element, its
Described in reduce carrier gas comprise reducibility gas；
Heat described mixed gas so that described Silicon chloride. gas reduction is elemental silicon by described reducibility gas, and shape
Become wherein said elemental silicon deposition Si-C composite material on the carbon material.
Method the most according to claim 1, it is characterised in that described reducibility gas selects free the following composition
Group: acetylene, hydrogen, methane, carbon monoxide, ammonia or combinations thereof.
Method the most according to claim 1, it is characterised in that described reducibility gas is acetylene.
Method the most according to claim 1, it is characterised in that described material with carbon element is graphite or by entering biological material
The biomass sources material with carbon element that row pre-treatment obtains.
Method the most according to claim 4, it is characterised in that described biological material selects free the following composition
Group: straw, rice husk, Folium Bambusae, corn cob or combinations thereof.
Method the most according to claim 4, it is characterised in that described pre-treatment includes:
Described biological material is pulverized；
Described biological material is carried out acid boil；
Described biological material is carried out carbonization treatment；
With the biological material after hydrofluoric acid clean carbonization treatment, it is thus achieved that biomass sources material with carbon element.
7. the Si-C composite material that prepared by a method according to claim 1.
Si-C composite material the most according to claim 7, it is characterised in that silicone content is in the range of 10-50 weight %.
Si-C composite material the most according to claim 7, it is characterised in that described material with carbon element is graphite or by biology
Material carries out the biomass sources material with carbon element of pre-treatment acquisition, the group of described biological material choosing free the following composition: straw
Stalk, rice husk, Folium Bambusae, corn cob or combinations thereof.
10., for a negative pole for lithium ion battery, described negative pole comprises Si-C composite material according to claim 7.
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