CN105552330A - Surface treatment method for graphite, application of graphite, preparation method and apparatus for porous electrode, graphite and silicon composite material and preparation method for composite material - Google Patents
Surface treatment method for graphite, application of graphite, preparation method and apparatus for porous electrode, graphite and silicon composite material and preparation method for composite material Download PDFInfo
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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
- H01M4/362—Composites
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- H01—ELECTRIC ELEMENTS
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- 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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- 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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- 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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- 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
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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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
- H01M4/36—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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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Abstract
The invention discloses a surface treatment method for graphite, an application of the graphite, a preparation method and apparatus for a porous electrode, a graphite and silicon composite material and a preparation method for the composite material. The treatment method comprises the steps of putting the graphite into an oxygen-containing atmosphere and performing high-temperature oxidation treatment on the graphite; and obtaining the graphite subjected to surface treatment by controlling the oxygen concentration, the reaction temperature and the reaction time. The treatment method is used for improving the chemical activity of the surface of the graphite and increasing the nucleation probability and loading capacity of the material on the surface of the graphite in an electrochemical reaction. The preparation method for the electrode comprises the step of preparing the electrode based on the graphite subjected to surface treatment. The preparation method and apparatus for the electrode can be used for preparing the electrode. The composite material is prepared based on the graphite subjected to surface treatment. The preparation method for the composite material can prepare the composite material. The loading capacity of silicon on the surface of the graphite in the composite material is increased, and the first-week electrochemical capacity of the composite material is increased when the composite material serves as a negative electrode material of a lithium ion battery.
Description
Technical field
The present invention relates to the processing technical field of graphite material, particularly relate to a kind of Graphite processing method and purposes, the preparation method of porous electrode and device, graphite and silicon composite and preparation method thereof.
Background technology
Graphite is a kind of multifunctional material, is widely used in every field with the conduction of its excellence, heat conduction and lubricating property.In recent years, graphite, due to cheap, environmental friendliness, stable electrochemical property, is widely used in commercial Li-ion battery as negative material.The crystal structure of graphite is six side's stratiforms, forms covalent bond with carbon atom each in layer and surrounding 3 carbon atoms with sp2 hydridization, and binding ability is very strong, and containing a large amount of free electrons in layer; Then combined by relatively weak Van der Waals force between layers.The surface of graphite, the face being parallel to graphite linings is basal plane (basalplane), and the edge that basal plane stops is called as edge surface (edgeplane).The special crystal structure of graphite result in the physicochemical properties of its different surfaces, and particularly electrochemical properties difference is huge.There are some researches show, edge surface (edgeplane) the electrochemical reaction activity on the surface of graphite is very high, and the reactivity of basal plane (basalplane) is then very low.The people such as MichaelP.Zach (Science., 2000,290,2120.) utilize the difference of the electro-chemical activity of the different crystal face of graphite surface just, make MoO
xonly also prepare Mo nano wire thus at the edge surface electrochemical deposition of graphite.Separately there are some researches show, the number closely related with the defect concentration on its surface (J.Phys.Chem.B2003,107,451.) in the electro-chemical activity site of graphite basal plane.Graphite is used for lubriation material and fuel-cell catalyst, it is being carried out to the process such as copper coating, cobalt (CN201110073830; CN201310391050) before, need to carry out surface coarsening process to it, to promote the load capacity of metal at graphite surface.Molten-salt electrolysis is a kind of method (Nat.Mater., 2003,2,397.) preparing nano-silicon and composite material thereof having industrialization potential of rising in recent years.The method is with melting CaCl
2deng material as molten salt electrolyte, with the SiO of cheapness
2as raw material (raw material), by applying certain curtage between negative electrode and anode, utilize electrochemical reducting reaction directly by SiO
2in oxygen remove, thus nano-silicon and composite material thereof can be prepared.The method, because low in raw material price, reaction temperature are relatively low and can prepare the silicon of nano-scale, is paid close attention in recent years widely.Applicant attempts preparing silicon and graphite composite material in employing fused salt electrolysis process and also wishes to find when using it for height ratio capacity lithium ion battery negative material, silicon is very low at the probability of graphite surface forming core, and most of silicon can only grow at rejected region place forming cores such as the edge of graphite or rough surface; Cause the load capacity of graphite surface silicon less, the electrochemistry capacitance of material is lower.Therefore, need to carry out surface treatment to graphite, alligatoring is carried out to graphite surface, to increase the electrochemical reaction avtive spot on its surface.
Surface-treated method carried out to graphite the having the method such as solwution method, plasma bombardment of bibliographical information.Graphite is generally immersed in the solution containing the strong oxidizer such as red fuming nitric acid (RFNA), the concentrated sulfuric acid by solwution method carries out oxidation processes (J.Electrochem.Soc., 1997,144,2968.) to graphite surface.But solwution method generally needs follow-up loaded down with trivial details cleaning and drying steps to remove liquid oxidizer and moisture.Plasma bombardment method adopts high-octane oxygen, argon plasma, can be processed (Appl.Phys.Lett., 1999,75,193.) by physical etchings effect to graphite surface, although controllability is fine, but needs instrument costly.
Summary of the invention
In view of this, the invention provides a kind of Graphite processing method and purposes, the preparation method of porous electrode and device, graphite and silicon composite and preparation method thereof, thus be more suitable for practicality.
In order to reach above-mentioned first object, Graphite processing method and technology scheme provided by the invention is as follows:
Graphite processing method provided by the invention comprises the following steps:
Graphite is placed in the atmosphere containing oxygen, high temperature oxidation process is carried out to graphite;
Surface treated graphite is obtained by control oxygen concentration, reaction temperature, reaction time.
Graphite processing method provided by the invention also can be applied to the following technical measures to achieve further.
As preferably, described the method that graphite carries out high temperature oxidation process to be comprised the following steps:
Be warming up to the temperature of a setting;
The time of constant temperature setting under the temperature conditions of described setting;
Stop heating and the atmosphere applied containing oxygen described in inert gas replacement, until the temperature of described graphite is reduced to room temperature.
As preferably, the surface topography of described surface treated graphite is selected from the one in terrace type, zigzag, hole, hole shape.
As preferably, described is 1% ~ 100% containing the span of the volume fraction of oxygen in the atmosphere of oxygen.
As preferably, the span of described reaction temperature is 500 DEG C ~ 800 DEG C.
As preferably, the span of described reaction temperature is 550 DEG C ~ 700 DEG C.
In order to reach above-mentioned second object, the technical scheme of the purposes of Graphite processing method provided by the invention is as follows:
The purposes of Graphite processing method provided by the invention comprises the chemically active purposes for promoting graphite surface; With, for promoting the nucleation probability of material at graphite surface and the purposes of load capacity in electrochemical reaction.
In order to reach above-mentioned 3rd object, preparation method's technical scheme of porous electrode provided by the invention is as follows:
The preparation method of porous electrode provided by the invention comprises the following steps:
Xiang Shuizhong adds SiO
2powder, first time is stirred to and forms SiO
2suspension-turbid liquid;
To described SiO
2add the surface treated graphite that arbitrary described method process obtains in claim 1 ~ 6 in suspension-turbid liquid, and second time stirs, obtain the SiO in paste
2with the mixture of surface treated graphite;
Dry the described SiO in paste
2with the mixture of surface treated graphite;
By the described SiO in paste
2be ground into containing SiO with the mixture of described surface treated graphite
2with the powder of surface treated graphite;
Compacting is described containing SiO
2with the powder of surface treated graphite, make it to be shaped to described porous electrode, the constituent of described porous electrode is SiO
2with surface treated graphite.
The preparation method of porous electrode provided by the invention also can be applied to the following technical measures to achieve further.
As preferably, described water is deionized water.
As preferably, described SiO
2powder is vapor phase method SiO
2, D90≤50nm.
As preferably, dry the described SiO in paste
2during mixture with surface treated graphite, the span of bake out temperature is 100 DEG C ~ 180 DEG C, and the span of drying time is 30h ~ 60h.
As preferably, containing SiO described in compacting
2during powder with surface treated graphite, the span of pressure is 160MPa ~ 200MPa, and the span of dwell time is 8min ~ 20min.
As preferably, described first time stirs and comprises first stirring at low speed high-speed stirred again.
As preferably, described second time stirs and comprises first stirring at low speed high-speed stirred again.
In order to reach above-mentioned 4th object, the preparation facilities technical scheme of porous electrode provided by the invention is as follows:
The preparation facilities of porous electrode provided by the invention comprises container, agitating device, drying unit, reducing mechanism and compression molding device;
Described container is used for accommodating water, SiO
2powder, surface treated graphite;
Described agitating device stirs and second time stirring for performing first time;
Described drying unit is for drying the SiO in paste
2with the mixture of surface treated graphite;
Described reducing mechanism is used for the described SiO in paste
2be ground into containing SiO with the mixture of described surface treated graphite
2with the powder of surface treated graphite;
Described compression molding device is described containing SiO for suppressing
2with the powder of surface treated graphite, make it to be shaped to described porous electrode.
The preparation facilities of porous electrode provided by the invention also can be applied to the following technical measures to achieve further.
As preferably, described agitating device is planetary stirring machine, and described container is the batch can of described planetary stirring machine.
As preferably, described drying unit is baking oven.
As preferably, described reducing mechanism is mechanical crusher.
As preferably, the pressure that described compression molding device is selected is isostatic cool pressing.
In order to reach above-mentioned 5th object, graphite provided by the invention and silicon composite technical scheme as follows:
Graphite in ink provided by the invention and silicon composite is through the surface treated graphite that Graphite processing method provided by the invention process obtains.
In order to reach above-mentioned 6th object, graphite provided by the invention and silicon composite to prepare forwarding method technical scheme as follows:
The preparation method of graphite provided by the invention and silicon composite comprises the following steps:
The porous electrode prepared with the preparation method of porous electrode provided by the invention is negative electrode, and graphite is anode, and described negative electrode and anode are placed in molten salt electrolyte;
Constant current is applied, by SiO between described negative electrode and anode
2be reduced to Si, i.e. obtained described graphite and silicon composite.
The preparation method of graphite provided by the invention and silicon composite also can be applied to the following technical measures to achieve further.
As preferably, the specification of described anode is greater than the specification of described negative electrode.
As preferably, the specification of described negative electrode is 50mm × 50mm × 5mm square piece.
As preferably, the specification of described anode is 100mm × 100mm × 10mm square piece.
As preferably, the span of the spacing between described negative electrode and positive electrode is 3cm ~ 10cm.
As preferably, the spacing between described negative electrode and positive electrode is 5cm.
As preferably, described molten salt electrolyte is melting CaCl
2.
As preferably, described melting CaCl
2the span of temperature is 782 DEG C ~ 1599 DEG C.
As preferably, described melting CaCl
2temperature be 850 DEG C.
As preferably, described constant current is 5A.
Graphite processing method provided by the invention utilizes O
2as oxidant, can directly adopt air as reacting gas, after reacting with graphite, products therefrom be CO, CO
2deng gas, when reaction compartment is enough large, CO, CO
2there is no toxic and side effect Deng gas, and product is without the need to numerous and diverse flow processs such as cleaning, dryings; In addition, Graphite processing method provided by the invention only needs to control oxygen concentration, reaction temperature, reaction time can realize processing graphite surface, low for equipment requirements, with low cost, simple to operate, condition is easily controlled, and is conducive to carrying out large-scale surface process to graphite material.
Graphite processing method provided by the invention can be used in promoting the chemism of graphite surface and promotes material in electrochemical reaction in the nucleation probability of graphite surface and load capacity.
Using the obtained porous electrode of the preparation method of porous electrode provided by the invention and preparation facilities as negative electrode, in the graphite produced and silicon composite, the load capacity of graphite surface silicon is higher, also higher as head week electrochemistry capacitance during lithium ion battery negative material with it.
Accompanying drawing explanation
By reading hereafter detailed description of the preferred embodiment, various other advantage and benefit will become cheer and bright for those of ordinary skill in the art.Accompanying drawing only for illustrating the object of preferred implementation, and does not think limitation of the present invention.And in whole accompanying drawing, represent identical parts by identical reference symbol.In the accompanying drawings:
The general steps flow chart of the Graphite processing method that Fig. 1 provides for the embodiment of the present invention one;
The concrete steps flow chart of the Graphite processing method that Fig. 2 provides for the embodiment of the present invention two;
The flow chart of steps of the preparation method of the porous electrode that Fig. 3 provides for the embodiment of the present invention three;
The schematic diagram of the preparation facilities of the porous electrode that Fig. 4 provides for the embodiment of the present invention four;
The flow chart of steps of the preparation method of the graphite that Fig. 5 provides for the embodiment of the present invention six and silicon composite;
Fig. 6 is amplified to the scanning electron microscope diagram sheet after a less multiple for not surface treated graphite that the embodiment of the present invention seven provides;
Fig. 7 is amplified to the scanning electron microscope diagram sheet after a larger multiple for not surface treated graphite that the embodiment of the present invention seven provides;
The scanning electron microscope diagram sheet of the graphite obtained after the Graphite processing method process that the embodiment of the present invention one provides that Fig. 8 provides for the embodiment of the present invention seven;
The scanning electron microscope diagram sheet of the graphite obtained after the Graphite processing method process that the embodiment of the present invention one provides that Fig. 9 provides for the embodiment of the present invention eight;
The scanning electron microscope diagram sheet of the graphite obtained after the Graphite processing method process that the embodiment of the present invention one provides that Figure 10 provides for the embodiment of the present invention nine;
The scanning electron microscope diagram sheet of the graphite obtained after the Graphite processing method process that the embodiment of the present invention one provides that Figure 11 provides for the embodiment of the present invention ten;
The scanning electron microscope diagram sheet of the graphite obtained after the Graphite processing method process that the embodiment of the present invention one provides that Figure 12 provides for the embodiment of the present invention 11;
The scanning electron microscope diagram sheet of the graphite obtained after the Graphite processing method process that the embodiment of the present invention one provides that Figure 13 provides for the embodiment of the present invention 12;
The scanning electron microscope diagram sheet of the graphite obtained after the Graphite processing method process that the embodiment of the present invention one provides that Figure 14 provides for the embodiment of the present invention 13;
The scanning electron microscope diagram sheet of the graphite obtained after the Graphite processing method process that the embodiment of the present invention one provides that Figure 15 provides for the embodiment of the present invention 14;
The scanning electron microscope diagram sheet of the graphite obtained after the Graphite processing method process that the embodiment of the present invention one provides that Figure 16 provides for the embodiment of the present invention 15;
The scanning electron microscope diagram sheet of the graphite that the preparation method of the graphite provided by the embodiment of the present invention six that Figure 17 provides for the embodiment of the present invention 16 and silicon composite prepares and silicon composite;
The scanning electron microscope diagram sheet of the graphite that Figure 18 provides for comparative example of the present invention and silicon composite.
Embodiment
The present invention, for solving prior art Problems existing, provides a kind of Graphite processing method and purposes, the preparation method of porous electrode and device, graphite and silicon composite and preparation method thereof, thus is more suitable for practicality.
For further setting forth the present invention for the technological means reaching predetermined goal of the invention and take and effect, below in conjunction with accompanying drawing and preferred embodiment, to the Graphite processing method proposed according to the present invention and purposes, the preparation method of porous electrode and device, graphite and silicon composite and preparation method thereof, its embodiment, structure, feature and effect thereof, be described in detail as follows.In the following description, the not necessarily same embodiment that different " embodiment " or " embodiment " refers to.In addition, special characteristic, structure or feature in one or more embodiment can be combined by any suitable form.
Term "and/or" herein, being only a kind of incidence relation describing affiliated partner, can there are three kinds of relations in expression, such as, A and/or B, concrete is interpreted as: can include A and B simultaneously, can individualism A, also can individualism B, above-mentioned three kinds of any one situations can be possessed.
Embodiment one
See accompanying drawing 1, the Graphite processing method that the embodiment of the present invention one provides comprises the following steps:
Step 11: graphite is placed in the atmosphere containing oxygen, high temperature oxidation process is carried out to graphite;
Step 12: obtain surface treated graphite by control oxygen concentration, reaction temperature, reaction time.
The Graphite processing method that the embodiment of the present invention one provides utilizes O
2as oxidant, can directly adopt air as reacting gas, after reacting with graphite, products therefrom be CO, CO
2deng gas, when reaction compartment is enough large, CO, CO
2there is no toxic and side effect Deng gas, and product is without the need to numerous and diverse flow processs such as cleaning, dryings; In addition, Graphite processing method provided by the invention only needs to control oxygen concentration, reaction temperature, reaction time can realize processing graphite surface, low for equipment requirements, with low cost, simple to operate, condition is easily controlled, and is conducive to carrying out large-scale surface process to graphite material.
Wherein, the surface topography of surface treated graphite is selected from the one in terrace type, zigzag, hole, hole shape.
Wherein, be 1% ~ 100% containing the span of the volume fraction of oxygen in the atmosphere of oxygen.
Wherein, the span of reaction temperature is 500 DEG C ~ 800 DEG C.
Embodiment two
As a kind of concrete implementation of the Graphite processing method that the embodiment of the present invention one provides, in the Graphite processing method that the embodiment of the present invention two provides, the method for graphite being carried out to high temperature oxidation process comprises the following steps:
Step 21: the temperature being warming up to a setting;
Step 22: the time of constant temperature setting under the temperature conditions of setting;
Step 23: stop heat and apply the atmosphere that inert gas replacement contains oxygen, until the temperature reduction room temperature of graphite.
In the present embodiment, the span of reaction temperature is 550 DEG C ~ 700 DEG C.
Said temperature scope is preferred temperature range.When temperature is lower than 550 DEG C, because graphite oxidation reaction rate is comparatively slow, reaching identical surface treatment effect needs longer time and higher oxygen content; When temperature is higher than 700 DEG C, because graphite oxidation reaction is too violent, needs strict control reaction time and oxygen content, be comparatively difficult to the effect of accurate control surface process.
The purposes of the Graphite processing method that the embodiment of the present invention one or embodiment two provide comprises the chemically active purposes for promoting graphite surface; For promoting the nucleation probability of material at graphite surface and the purposes of load capacity in electrochemical reaction.
Embodiment three
See accompanying drawing 3, the preparation method of the porous electrode that the embodiment of the present invention three provides comprises the following steps:
Step 31: Xiang Shuizhong adds SiO
2powder, first time is stirred to and forms SiO
2suspension-turbid liquid;
Step 32: to SiO
2add the surface treated graphite that method process arbitrary in claim 1 ~ 6 obtains in suspension-turbid liquid, and second time stirs, obtain the SiO in paste
2with the mixture of surface treated graphite;
Step 33: dry the SiO in paste
2with the mixture of surface treated graphite;
Step 34: by the SiO in paste
2be ground into containing SiO with the mixture of surface treated graphite
2with the powder of surface treated graphite;
Step 35: compacting is containing SiO
2with the powder of surface treated graphite, make it to be shaped to porous electrode, the constituent of porous electrode is SiO
2with surface treated graphite.
Wherein, water is deionized water.Thus avoid water intermediate ion to impact result of the test.
Wherein, SiO
2powder is vapor phase method SiO
2, D90≤50nm.
Wherein, the SiO in paste is dried
2during mixture with surface treated graphite, the span of bake out temperature is 100 DEG C ~ 180 DEG C, and the span of drying time is 30h ~ 60h.Can choose relevant parameter according to the time of bake out temperature and correspondence, bake out temperature is high, then drying time is short; Bake out temperature is low, then drying time is long.
Wherein, compacting is containing SiO
2during powder with surface treated graphite, the span of pressure is 160MPa ~ 200MPa, and the span of dwell time is 8min ~ 20min.Can choose relevant parameter according to the dwell time of pressure and correspondence, pressure is high, then the dwell time is short; Pressure is low, then the dwell time is long.
Wherein, first time stirs and comprises first stirring at low speed high-speed stirred again.The object of stirring at low speed makes SiO
2powder tentatively mixes with water, and the object of high-speed stirred makes SiO
2powder fully mixes with water.
Wherein, second time stirs and comprises first stirring at low speed high-speed stirred again.The object of stirring at low speed makes the powder of surface treated graphite and above-mentioned SiO well-mixed with water
2powder tentatively mixes, and the object of high-speed stirred makes the powder of graphite and above-mentioned SiO well-mixed with water
2powder fully mixes.
Embodiment four
See accompanying drawing 4, the preparation facilities of the porous electrode that the embodiment of the present invention four provides comprises container, agitating device, drying unit, reducing mechanism and compression molding device; Container is used for accommodating water, SiO
2powder, surface treated graphite; Agitating device stirs and second time stirring for performing first time; Drying unit is for drying the SiO in paste
2with the mixture of surface treated graphite; Reducing mechanism is used for the SiO in paste
2be ground into containing SiO with the mixture of surface treated graphite
2with the powder of surface treated graphite; Compression molding device is used for compacting containing SiO
2with the powder of surface treated graphite, make it to be shaped to porous electrode.
In the present embodiment, agitating device is planetary stirring machine, and container is the batch can of planetary stirring machine; Drying unit is baking oven; Reducing mechanism is mechanical crusher; The pressure that compression molding device is selected is isostatic cool pressing.
Embodiment five
The surface treated graphite that the Graphite processing method process that graphite in the graphite that the embodiment of the present invention five provides and silicon composite is through the embodiment of the present invention one or embodiment two to be provided obtains.
Embodiment six
See accompanying drawing 5, the preparation method of the graphite that the embodiment of the present invention six provides and silicon composite comprises the following steps:
Step 61: the porous electrode prepared with the preparation method of porous electrode provided by the invention is negative electrode, graphite is anode, and negative electrode and anode are placed in molten salt electrolyte;
Step 62: apply constant current between a cathode and an anode, by SiO
2be reduced to Si, i.e. obtained graphite and silicon composite.
Wherein, the specification of anode is greater than the specification of negative electrode.In this case, SiO
2reduction reaction is more thorough.
In the present embodiment, the specification of negative electrode is 50mm × 50mm × 5mm square piece, and the specification of anode is 100mm × 100mm × 10mm square piece.
Wherein, the span of the spacing between negative electrode and positive electrode is 3cm ~ 10cm, thus ensures that reaction is carried out smoothly.In the present embodiment, the spacing between negative electrode and positive electrode is 5cm.
Wherein, molten salt electrolyte is melting CaCl
2.
Wherein, melting CaCl
2the span of temperature is 782 DEG C ~ 1599 DEG C.Wherein, 782 DEG C is CaCl
2fusing point, 1599 DEG C is CaCl
2boiling point, between these two temperature, CaCl
2be in molten condition.In the present embodiment, melting CaCl
2temperature be 850 DEG C.
In the present embodiment, constant current is 5A.
Using the obtained porous electrode of the preparation method of porous electrode provided by the invention and preparation facilities as negative electrode, in the graphite produced and silicon composite, the load capacity of graphite surface silicon is higher, also higher as head week electrochemistry capacitance during lithium ion battery negative material with it.
Embodiment seven ~ embodiment 15
Embodiment 16 and comparative example
As can be seen from embodiment 16 and comparative example form, Figure 17, Figure 18, after adopting the inventive method to carry out surface treatment to graphite, due to graphite surface alligatoring, electrochemical reaction avtive spot increases, in the composite material of graphite prepared by molten-salt electrolysis and silicon, the load capacity of the silicon of graphite surface gets a promotion.After adopting the inventive method to carry out preliminary treatment to graphite, because graphite surface silicon load capacity increases, during as lithium ion battery negative material, first all electrochemistry capacitances reach 930mAh/g; And not surface treated graphite, when corresponding graphite and silicon composite are as lithium ion battery negative material, first all electrochemistry capacitances are lower, are only 707mAh/g.
Although describe the preferred embodiments of the present invention, those skilled in the art once obtain the basic creative concept of cicada, then can make other change and amendment to these embodiments.So claims are intended to be interpreted as comprising preferred embodiment and falling into all changes and the amendment of the scope of the invention.
Obviously, those skilled in the art can carry out various change and modification to the present invention and not depart from the spirit and scope of the present invention.Like this, if these amendments of the present invention and modification belong within the scope of the claims in the present invention and equivalent technologies thereof, then the present invention is also intended to comprise these change and modification.
Claims (10)
1. a Graphite processing method, is characterized in that, comprises the following steps:
Graphite is placed in the atmosphere containing oxygen, high temperature oxidation process is carried out to graphite;
Surface treated graphite is obtained by control oxygen concentration, reaction temperature, reaction time;
As preferably, described the method that graphite carries out high temperature oxidation process to be comprised the following steps:
Be warming up to the temperature of a setting;
The time of constant temperature setting under the temperature conditions of described setting;
Stop heating and the atmosphere applied containing oxygen described in inert gas replacement, until the temperature of described graphite is reduced to room temperature;
As preferably, the surface topography of described surface treated graphite is selected from the one in terrace type, zigzag, hole, hole shape;
As preferably, described is 1% ~ 100% containing the span of the volume fraction of oxygen in the atmosphere of oxygen;
As preferably, the span of described reaction temperature is 500 DEG C ~ 800 DEG C;
As preferably, the span of described reaction temperature is 550 DEG C ~ 700 DEG C.
2. Graphite processing method according to claim 1 is for promoting the chemically active purposes of graphite surface.
3. Graphite processing method according to claim 1 is for promoting the nucleation probability of material at graphite surface and the purposes of load capacity in electrochemical reaction.
4. a preparation method for porous electrode, is characterized in that, comprises the following steps:
Xiang Shuizhong adds SiO
2powder, first time is stirred to and forms SiO
2suspension-turbid liquid;
To described SiO
2add the surface treated graphite obtained through method process according to claim 1 in suspension-turbid liquid, and second time stirs, obtain the SiO in paste
2with the mixture of surface treated graphite;
Dry the described SiO in paste
2with the mixture of surface treated graphite;
By the described SiO in paste
2be ground into containing SiO with the mixture of described surface treated graphite
2with the powder of surface treated graphite;
Compacting is described containing SiO
2with the powder of surface treated graphite, make it to be shaped to described porous electrode, the constituent of described porous electrode is SiO
2with surface treated graphite;
As preferably, described water is deionized water;
As preferably, described SiO
2powder is vapor phase method SiO
2, D90≤50nm;
As preferably, dry the described SiO in paste
2during mixture with surface treated graphite, the span of bake out temperature is 100 DEG C ~ 180 DEG C, and the span of drying time is 30h ~ 60h;
As preferably, containing SiO described in compacting
2during powder with surface treated graphite, the span of pressure is 160MPa ~ 200MPa, and the span of dwell time is 8min ~ 20min;
As preferably, described first time stirs and comprises first stirring at low speed high-speed stirred again;
As preferably, described second time stirs and comprises first stirring at low speed high-speed stirred again.
5. a preparation facilities for porous electrode, is characterized in that, comprises container, agitating device, drying unit, reducing mechanism and compression molding device;
Described container is used for accommodating water, SiO
2powder, surface treated graphite;
Described agitating device stirs and second time stirring for performing first time;
Described drying unit is for drying the SiO in paste
2with the mixture of surface treated graphite;
Described reducing mechanism is used for the described SiO in paste
2be ground into containing SiO with the mixture of described surface treated graphite
2with the powder of surface treated graphite;
Described compression molding device is described containing SiO for suppressing
2with the powder of surface treated graphite, make it to be shaped to described porous electrode;
As preferably, described agitating device is planetary stirring machine, and described container is the batch can of described planetary stirring machine;
As preferably, described drying unit is baking oven;
As preferably, described reducing mechanism is mechanical crusher;
As preferably, the pressure that described compression molding device is selected is isostatic cool pressing.
6. graphite and a silicon composite, is characterized in that, the graphite in described graphite and silicon composite is through the surface treated graphite that method process according to claim 1 obtains.
7. the preparation method of graphite according to claim 6 and silicon composite, is characterized in that, comprises the following steps:
The porous electrode prepared with method according to claim 4 is negative electrode, and graphite is anode, and described negative electrode and anode are placed in molten salt electrolyte;
Constant current is applied, by SiO between described negative electrode and anode
2be reduced to Si, i.e. obtained described graphite and silicon composite.
8. the preparation method of graphite according to claim 7 and silicon composite, is characterized in that, the specification of described anode is greater than the specification of described negative electrode;
As preferably, the specification of described negative electrode is 50mm × 50mm × 5mm square piece;
As preferably, the specification of described anode is 100mm × 100mm × 10mm square piece;
As preferably, the span of the spacing between described negative electrode and positive electrode is 3cm ~ 10cm;
As preferably, the spacing between described negative electrode and positive electrode is 5cm.
9. the preparation method of graphite according to claim 8 and silicon composite, is characterized in that, described molten salt electrolyte is melting CaCl
2;
As preferably, described melting CaCl
2the span of temperature is 782 DEG C ~ 1599 DEG C;
As preferably, described melting CaCl
2temperature be 850 DEG C.
10. the preparation method of graphite according to claim 9 and silicon composite, is characterized in that, described constant current is 5A.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107732195A (en) * | 2017-10-10 | 2018-02-23 | 国联汽车动力电池研究院有限责任公司 | A kind of graphite modified method and graphite/silicon composite |
| CN111384380A (en) * | 2018-12-29 | 2020-07-07 | 上海杉杉科技有限公司 | Silicon-carbon negative electrode material, preparation method and application thereof, and lithium ion battery prepared from silicon-carbon negative electrode material |
| CN113276494A (en) * | 2021-04-30 | 2021-08-20 | 北京化工大学 | Preparation method of graphite film/metal composite heat conducting cable |
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|---|---|---|---|---|
| CN103107315A (en) * | 2011-11-10 | 2013-05-15 | 北京有色金属研究总院 | Nano silicon-carbon composite material and preparation method thereof |
| CN103303907A (en) * | 2013-04-28 | 2013-09-18 | 南昌大学 | Surface modification method for spherical graphite negative material |
| CN104852023A (en) * | 2015-04-01 | 2015-08-19 | 廖楚宏 | Carbon composite material and preparation method therefor |
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2015
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103107315A (en) * | 2011-11-10 | 2013-05-15 | 北京有色金属研究总院 | Nano silicon-carbon composite material and preparation method thereof |
| CN103303907A (en) * | 2013-04-28 | 2013-09-18 | 南昌大学 | Surface modification method for spherical graphite negative material |
| CN104852023A (en) * | 2015-04-01 | 2015-08-19 | 廖楚宏 | Carbon composite material and preparation method therefor |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107732195A (en) * | 2017-10-10 | 2018-02-23 | 国联汽车动力电池研究院有限责任公司 | A kind of graphite modified method and graphite/silicon composite |
| CN111384380A (en) * | 2018-12-29 | 2020-07-07 | 上海杉杉科技有限公司 | Silicon-carbon negative electrode material, preparation method and application thereof, and lithium ion battery prepared from silicon-carbon negative electrode material |
| CN111384380B (en) * | 2018-12-29 | 2022-02-01 | 上海杉杉科技有限公司 | Silicon-carbon negative electrode material, preparation method and application thereof, and lithium ion battery prepared from silicon-carbon negative electrode material |
| CN113276494A (en) * | 2021-04-30 | 2021-08-20 | 北京化工大学 | Preparation method of graphite film/metal composite heat conducting cable |
| CN113276494B (en) * | 2021-04-30 | 2023-02-28 | 北京化工大学 | Preparation method of graphite film/metal composite heat conducting cable |
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