CN107507972A - Preparation method, silicon-carbon cathode material and the lithium ion battery of silicon-carbon cathode material - Google Patents
Preparation method, silicon-carbon cathode material and the lithium ion battery of silicon-carbon cathode material Download PDFInfo
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- CN107507972A CN107507972A CN201710759298.8A CN201710759298A CN107507972A CN 107507972 A CN107507972 A CN 107507972A CN 201710759298 A CN201710759298 A CN 201710759298A CN 107507972 A CN107507972 A CN 107507972A
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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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- 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
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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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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention belongs to technical field of lithium ion, is related to a kind of preparation method of silicon-carbon cathode material, silicon-carbon cathode material and lithium ion battery.The preparation method of silicon-carbon cathode material provided by the invention, comprises the following steps：Using silicon alloy powder as raw material, through pickling processes, after removing remaining metal in silicon alloy powder in addition to silicon, porous silicon is obtained；Porous silicon is put into carbon precursor, carries out carbon coating processing, forms the Si-C composite material with carbon coating layer；Si-C composite material is subjected to carbonization treatment, obtains silicon-carbon cathode material.Present invention process is simple, easy to operate, and obtained silicon-carbon cathode material is provided simultaneously with the high storage lithium characteristic of silicon class material and the high circulation stability of carbons material, and specific capacity is high, good conductivity, good cycle.
Description
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of preparation method of silicon-carbon cathode material, silicon-carbon
Negative material and lithium ion battery.
Background technology
In existing secondary cell system, no matter from development space, or from the life-span, than energy, operating voltage and from
From the point of view of the technical indicators such as discharge rate, lithium ion battery is all current most competitive secondary cell.With electronics technology not
Disconnected development, higher requirement is it is also proposed to lithium ion battery, it is necessary to higher energy density, more preferable cycle life, more preferable
High/low temperature charge-discharge performance and security performance etc., this requires lithium ion battery to need to obtain into one with positive pole, negative material
Step ground development and perfection.
The more lithium ion battery negative material of current practice is carbon material, such as native graphite, graphitized intermediate-phase
Carbosphere etc..In non-carbon negative material, silicon has a high theoretical specific capacity, relatively low storage lithium response voltage platform, and
Distribution of the silicon in nature is very wide, and the content in the earth's crust is only second to oxygen, therefore silicon based anode material is a kind of great development
The novel high-energy material of prospect.However, the electronic conductivity and ionic conductivity of silicon are relatively low, cause the power of its electrochemical reaction
Learn poor-performing；The cyclical stability of common pure silicon is poor.And phase transformation and volumetric expansion of the silicon during lithiumation can produce
Larger stress, cause lead rupture efflorescence, resistance increase, cycle performance rapid drawdown.
Research currently for silicon based anode material is mainly to be pyrolyzed after silica flour is carried out into ball milling mixing with carbon source material, with
Silico-carbo composite is prepared, to alleviate the Study of Volume Expansion in battery charge and discharge process, improves the cyclicity of silica-base material
Energy.In existing silicon-carbon cathode material preparation process, there are two kinds of more conventional methods：First, using argent as catalysis
Three-dimensional porous silicon materials are made in the method for agent induced chemical corrosion, are then mixed with carbon source by the method for ball milling, sinter
The silicon carbon material of carbon coating is obtained afterwards；Second, be sintered using silicon monoxide under the conditions of argon gas, it is anti-using the disproportionation of itself
Silicon and silica should be generated, porous silicon is then prepared by the method for etching, finally by obtained mixture and carbon source by
Certain mass after being well mixed than being calcined.However, in existing silicon-carbon cathode material preparation method, also there is certain deficiency
Part, for example, high as catalyst cost using noble metal, the cost of silicon monoxide is also higher etc.；In addition, method operating procedure
Numerous and diverse, course of reaction is difficult to control, less stable, for improve discharge and recharge when silicon Study of Volume Expansion and unobvious.
In consideration of it, special propose the present invention.
The content of the invention
The first object of the present invention is to provide a kind of preparation method of silicon-carbon cathode material, and technique is simple, easy to operate, system
The silicon-carbon cathode material obtained is provided simultaneously with the high storage lithium characteristic of silicon class material and the high circulation stability of carbons material, effectively suppresses
The volumetric expansion of silicium cathode, specific capacity is high, has extended cycle life.
The second object of the present invention is to provide a kind of silicon-carbon cathode material, and the volume that can effectively suppress silicium cathode is swollen
It is swollen, there is excellent electric conductivity, and specific capacity is high, good cycle.
The third object of the present invention is to provide a kind of lithium ion battery, and the lithium ion battery specific capacity is high, cycle performance
It is good, electrochemical performance.
To achieve the above object, the technical solution adopted by the present invention is：
According to an aspect of the present invention, the present invention provides a kind of preparation method of silicon-carbon cathode material, including following step
Suddenly：
Using silicon alloy powder as raw material, through pickling processes, after removing remaining metal in silicon alloy powder in addition to silicon, obtain
To porous silicon；
The porous silicon is put into carbon precursor, carries out carbon coating processing, it is compound to form the silicon-carbon with carbon coating layer
Material；
The Si-C composite material is subjected to carbonization treatment, obtains silicon-carbon cathode material.
As further preferred technical scheme, the silicon alloy is silico-aluminum, Antaciron, Si-Mg alloy, copper silicon conjunction
Gold, silicon nickel alloy and one kind in silicomangan or at least two combination, preferably silico-aluminum, Antaciron and silicon magnesium close
One kind or at least two combination in gold, more preferably silico-aluminum；
Preferably, the particle size range of the silicon alloy powder is 20~70 μm, preferably 30~60 μm, is more preferably
35~55 μm；
Preferably, the mass fraction of silicon is 5%~20%, preferably 8%~15% in the silicon alloy powder, further
Preferably 10%~13%.
As further preferred technical scheme, before through pickling processes, in addition to the pulverization process step to raw material；
Preferably, pulverization process is carried out to raw material by the way of air-flow crushing；
Preferably, carry out first carrying out precomminution before air-flow crushing, the rotating speed of precomminution is 200~300rpm；
Preferably, the admission pressure of air-flow crushing is 0.4~0.6Mpa, and the pressure of crushing is 0.6~0.8Mpa；
Preferably, the particle size range of the powder obtained after air-flow crushing is 8~15 μm.
As further preferred technical scheme, described pickling processes include a pickling, filtering and rinsing；
Preferably, the pickling processes include a pickling, filtering, white picking and rinsing；
Preferably, a pickling using mass concentration be 2%~20% hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid and
In acetic acid solution it is a kind of or at least two combination, the time of a pickling is 10~60min；
Preferably, in the filtration step, the pore diameter range of filter substrate is 0.5~3 μm；
Preferably, the white picking using hydrofluoric acid solution that mass concentration is 3%~20%, hydrofluoric acid with it is double
One kind in the mixed solution or hydrofluoric acid of oxygen water and the mixed solution of nitric acid, the time of white picking is 5~30min；
Preferably, the rinsing is using deionized water, pure water or distilled water；
Preferably, dry step is also included after the rinse step, dry temperature is preferably 80~100 DEG C.
As further preferred technical scheme, the carbon precursor include polyvinyl alcohol, polyvinyl chloride, butadiene-styrene rubber breast,
In polymethyl methacrylate, polyacrylonitrile, phenolic resin, pitch, glucose, sucrose, cellulose, epoxy resin and starch
Any one or at least two combination.
As further preferred technical scheme, the processing of described carbon coating comprises the following steps：
By the porous silicon and carbon precursor according to 1：6~10 mass ratio mixing, after stirring 60~90min, ultrasound
Scattered 30~60min, then be dried, obtain the Si-C composite material with carbon coating layer；
Preferably, using magnetic agitation, the temperature of stirring is 20~30 DEG C for the stirring；
Preferably, the drying is using spray drying, and the pressure of spray drying is 0.2~0.4Mpa, inlet temperature
For 180~240 DEG C, outlet temperature is 120~180 DEG C.
As further preferred technical scheme, described carbonization treatment comprises the following steps：
The Si-C composite material is placed in heater, 30~60min is first purified under protective atmosphere, then with 5
~10 DEG C/min heating rate is warming up to 800~1000 DEG C, after being incubated 1~3h, is cooled to room temperature, obtains silicon-carbon cathode material
Material.
As further preferred technical scheme, the heater is in tube furnace, rotary furnace, batch-type furnace or roller kilns
It is a kind of；
Preferably, the protective atmosphere is one kind in nitrogen, helium, neon, argon gas, hydrogen or argon hydrogen gaseous mixture；
Preferably, the flow of the protective atmosphere is 40~60mL/min.
According to another aspect of the present invention, the present invention also provides a kind of silicon-carbon cathode material, by above-described silicon-carbon
The preparation method of negative material is made.
According to another aspect of the present invention, the present invention also provides a kind of lithium ion battery, including negative pole, the negative pole bag
Include above-described silicon-carbon cathode material.
Compared with prior art, the beneficial effects of the present invention are：
1st, porous type has been made by pickling processes, carbon coating processing and carbonization treatment using silicon alloy as raw material in the present invention
There is honey comb like silicon-carbon cathode material, alleviate the bulk effect in charge and discharge process, reduce electroactive material efflorescence
Obscission, so as to effectively increase the cyclical stability of lithium ion battery, service life length；Meanwhile improve silica-base material
Electric conductivity, improve the reversible specific capacity of material.
2nd, cost of material of the present invention is low, environment-friendly, and preparation process is easily operated, convenient control, and process conditions are simply easy
OK, energy consumption is low, and obtained silicon-carbon cathode material is provided simultaneously with the high storage lithium characteristic of silicon class material and the Gao Xun of carbons material
Ring stability, good conductivity, specific capacity is high, and kinetics performance is good, it is easy to accomplish industrialization, has on lithium ion battery
Good application prospect.
3rd, lithium ion battery and silicon-carbon cathode material provided by the invention, cost is low, stable performance, and specific capacity is high, leads
It is electrically good, have extended cycle life, electrochemical performance.
Brief description of the drawings
, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical scheme of the prior art
The required accompanying drawing used is briefly described in embodiment or description of the prior art, it should be apparent that, in describing below
Accompanying drawing is some embodiments of the present invention, for those of ordinary skill in the art, before creative work is not paid
Put, other accompanying drawings can also be obtained according to these accompanying drawings.
Fig. 1 is that the SEM for the silicon-carbon cathode material that the embodiment of the present invention 3 provides schemes (Scanning Electron
Microscope scanning electron microscope (SEM) photographs)；What Fig. 1 (a) and Fig. 1 (b) were represented respectively is at porous silicon and carbonization that pickling processes obtain
Manage the SEM figures of obtained silicon-carbon cathode material；
Fig. 2 is the cycle-index-electric discharge for the lithium ion battery that silicon-carbon cathode material prepared by the embodiment of the present invention 3 is made
Specific volume spirogram, abscissa are cycle-index, and ordinate is specific discharge capacity (mAhg- 1)。
Embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment and embodiment, but this area skill
Art personnel will be understood that following embodiments and embodiment are merely to illustrate the present invention, and be not construed as the model of the limitation present invention
Enclose.Based on the embodiment in the present invention, what those of ordinary skill in the art were obtained under the premise of creative work is not made
Every other embodiment, belongs to the scope of protection of the invention.Actual conditions person is indicated, is suggested according to normal condition or manufacturer
Condition carry out.Agents useful for same or the unreceipted production firm person of instrument, it is the conventional products that can be obtained by commercially available purchase.
In a first aspect, present embodiment provides a kind of preparation method of silicon-carbon cathode material, comprise the following steps：
Using silicon alloy powder as raw material, through pickling processes, after removing remaining metal in silicon alloy powder in addition to silicon, obtain
To porous silicon；
The porous silicon is put into carbon precursor, carries out carbon coating processing, it is compound to form the silicon-carbon with carbon coating layer
Material；
The Si-C composite material is subjected to carbonization treatment, obtains silicon-carbon cathode material.
By silicon-carbon cathode material made from the preparation method of silicon-carbon cathode material provided by the invention, can overcome existing
The defects of can not all meeting needs when the negative material of silicon materials and carbon material as lithium ion battery being used alone in technology, can
To give full play to the function of silicon and carbon, there is preferable structural stability.On the one hand, the superior electric conductivity of carbon-coating is make use of, more
The problem of having mended silicon grain poorly conductive, improve the electric conductivity of material；On the other hand, electrification is increased by silicon substrate material
Reaction interface is learned, improves the electrochemical reaction dynamic performance of material, improves the cycle performance of electrode, can prevent silicon core from crushing
It is scattered, effectively prevent composite and rupture crushing due to Volume Changes in charge and discharge process, improve silicon bulk effect, protect
The structural stability of material is demonstrate,proved.In addition, the table by the way that silicon in one layer of carbon-coating of silicon substrate material surface uniform load, can be improved
Face structure, reduce it and contacted with the direct of electrolyte, promote to form stable, thin and compact solid electrolyte in electrode surface
Film, improve electrode/electrolyte interface compatibility, and then improve the cycle performance of electrode.
The present invention using silicon alloy powder as raw material, its silicon alloy powder is preferably widely used on the market, preparation technology into
Ripe silicon alloy powder.With it is of the prior art in a manner of noble metal is catalyst etc. compared with, have cost of material it is low, operation
The advantages of process is more easily controlled, simple and easy, environment-friendly, and energy consumption is low.
Silicon alloy powder is carried out pickling processes by the present invention, on the one hand by remaining metal in addition to silicon in silicon alloy
It is dissolved in acid, and silicon does not dissolve in the acid, and then remaining metal in silicon alloy in addition to silicon is removed, on the other hand pass through acid attack
The mode of silicon, porous silicon powder is made.Then obtained porous silicon is carried out into silicon-carbon of the carbon coating formation with carbon coating layer to answer
Condensation material, then carry out high temperature cabonization processing, that is, obtain carbon silicium cathode material.So as to alleviate existing Si-C composite material system
The problems such as standby complex process, cost are high, and effect is undesirable.
In a kind of optional embodiment, the silicon alloy is silico-aluminum, Antaciron, Si-Mg alloy, copper silicon conjunction
Gold, silicon nickel alloy and one kind in silicomangan or at least two combination, preferably silico-aluminum, Antaciron and silicon magnesium close
One kind or at least two combination in gold, more preferably silico-aluminum；
Preferably, the particle size range of the silicon alloy powder is 20~70 μm, preferably 30~60 μm, is more preferably
35~55 μm；
Preferably, the mass fraction of silicon is 5%~20%, preferably 8%~15% in the silicon alloy powder, further
Preferably 10%~13%.
Silicon alloy in the present invention is using commercially available silicon alloy, it is preferred to use be to be widely used, prepare on the market
The eutectic silico-aluminum of technical maturity, have raw material sources extensive, be easy to get, cost is low, the characteristics of being easy to subsequent operation.
In a detailed embodiment, optionally, the particle diameter of silicon alloy powder is 20 μm, 25 μm, 30 μm, 35 μm, 40 μ
M, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm or 70 μm.
In a detailed embodiment, optionally, in silicon alloy powder the mass fraction of silicon for 5%, 6%, 7%,
8%th, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19% or 20%.
In a kind of optional embodiment, before through pickling processes, in addition to the pulverization process step to raw material；
Preferably, pulverization process is carried out to raw material by the way of air-flow crushing；
Preferably, carry out first carrying out precomminution before air-flow crushing, the rotating speed of precomminution is 200~300rpm, air-flow powder
Broken admission pressure is 0.4~0.6Mpa, and the pressure of air-flow crushing is 0.6~0.8Mpa；
Preferably, the particle size range of the powder obtained after air-flow crushing is 8~15 μm.
In view of the particle size range difference of commercially available silicon alloy powder is larger, further to improve subsequent treatment effect, need to lead to
Cross the method crushed further to crush raw material, to obtain required particle size range.It is preferably air-flow crushing that it, which is crushed,
Mode, convenient operation, good crushing effect.
In a detailed embodiment, optionally, the concrete operations of air-flow crushing are：(1) raw material is put into hopper；
(2) feed motor is opened, the rotating speed for adjusting twin-screw is 200rpm, 250rpm or 300rpm；(3) by twin-screw precomminution
Powder enters air-flow crushing chamber, and it is 0.4Mpa, 0.5Mpa or 0.6Mpa to control admission pressure, crushing pressure be 0.6Mpa,
0.7Mpa or 0.8Mpa；(4) powder after crushing is collected by cyclone separator and trapping system.
In a detailed embodiment, optionally, the particle diameter of the powder obtained after air-flow crushing is 8 μm, 9 μm, 10 μ
M, 11 μm, 12 μm, 13 μm, 14 μm or 15 μm.The particle size range of required powder can be obtained by adjusting the pressure of air-flow crushing.
In a kind of optional embodiment, described pickling processes include a pickling, filtering and rinsing；
Preferably, the pickling processes include a pickling, filtering, white picking and rinsing；
Preferably, a pickling using mass concentration be 2%~20% hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid and
In acetic acid solution it is a kind of or at least two combination, the time of a pickling is 10~60min, it is preferred to use mass concentration is
8%~15% hydrochloric acid or sulfuric acid, the time of a pickling is preferably 15~30min；
Preferably, in the filtration step, 0.5~3 μm of the pore diameter range of filter substrate, preferably 1~2 μm；
Preferably, the white picking using hydrofluoric acid solution that mass concentration is 3%~20%, hydrofluoric acid with it is double
One kind in the mixed solution or hydrofluoric acid of oxygen water and the mixed solution of nitric acid, the time of white picking is 5~30min；
Preferably, the rinsing is using deionized water, pure water or distilled water；
Preferably, dry step is also included after the rinse step, dry temperature is preferably 80~100 DEG C.
The pickling processes of the present invention can include a step of pickling, filtering and rinsing, obtained in order to further improve
Porous silicon purity, white picking can also be included, and white picking is carried out before rinsing, i.e., pickling processes are included once
The step of pickling, filtering, white picking and rinsing.Wherein, a pickling is different with the sour type used in white picking, so as to
Remaining metallic element in more effectively removal silicon alloy, and improve the purity of porous silicon.
In a detailed embodiment, optionally, pickling processes step is specially：(1) will be obtained by air-flow crushing
Powder be put into the hydrochloric acid, sulfuric acid or phosphoric acid solution that mass concentration is 2%, 5%, 8%, 10%, 15% or 20%, carry out one
Secondary pickling, time 10min, 15min, 20min, 25min, 30min, 40min, 50min or 60min；(2) use aperture for
0.5 μm, 1 μm, 1.5 μm, 2 μm or 3 μm of filter substrate (such as filter paper) is filtered；(3) deionized water, pure water or distillation are used
Water is rinsed；(4) it is put into vacuum drying chamber and is dried, dry temperature is 80 DEG C, 90 DEG C or 100 DEG C.
In a detailed embodiment, optionally, pickling processes step is specially：(1) will be obtained by air-flow crushing
Powder be put into the hydrochloric acid, sulfuric acid or phosphoric acid solution that mass concentration is 2%, 5%, 8%, 10%, 15% or 20%, carry out one
Secondary pickling, time 10min, 15min, 20min, 25min, 30min, 40min, 50min or 60min；(2) use aperture for
0.5 μm, 1 μm, 1.5 μm, 2 μm or 3 μm of filter substrate (such as filter paper) is filtered；(3) use mass concentration for 3%, 5%,
10%th, the mixed solution of the mixed solution of 15% or 20% hydrofluoric acid solution, hydrofluoric acid and hydrogen peroxide or hydrofluoric acid and nitric acid,
Carry out white picking, time 5min, 10min, 15min, 20min, 25min or 30min；(4) using deionized water, pure water or
Distilled water is rinsed；(5) it is put into vacuum drying chamber and is dried, dry temperature is 80 DEG C, 90 DEG C or 100 DEG C.
In a kind of optional embodiment, the carbon precursor include polyvinyl alcohol, polyvinyl chloride, butadiene-styrene rubber breast,
In polymethyl methacrylate, polyacrylonitrile, phenolic resin, pitch, glucose, sucrose, cellulose, epoxy resin, starch
Any one or at least two combination.
Preferably, carbon precursor is one kind in pitch, glucose, sucrose, cellulose or starch.
Carbon precursor and solvent are configured to carbon precursor solution, wherein solvent can be selected according to carbon precursor, only
Carbon precursor can be dissolved, can refer to prior art and selected and prepared.
In a kind of optional embodiment, described carbon coating processing step, it is specially：
By the porous silicon and carbon precursor according to 1：6~10 mass ratio mixing, after stirring 60~90min, ultrasound
Scattered 30~60min, then be dried, obtain the Si-C composite material with carbon coating layer；
Preferably, using magnetic agitation, the temperature of stirring is 20~30 DEG C for the stirring；
Preferably, the drying is using spray drying, and the pressure of spray drying is 0.2~0.4Mpa, inlet temperature
For 180~240 DEG C, outlet temperature is 120~180 DEG C.
The purpose for carrying out carbon coating is in order to form carbon coating layer on the surface of porous silicon, so as to form composite.
In a detailed embodiment, optionally, carbon coating processing step is specially：(1) by body before porous silicon and carbon
Body is according to 1：6、1：7、1：8、1：9 or 1：10 mass ratio mixing, under the conditions of temperature is 20~30 DEG C (room temperature), carries out magnetic
Power stirs 60min, 70min, 80min or 90min, and ultrasonic disperse 30min, 40min, 50min or 60min, (2) are dry using spraying
Dry mode is dried, and the pressure of spray drying is 0.2Mpa, 0.3Mpa or 0.4Mpa, inlet temperature is 180 DEG C, 190 DEG C,
200 DEG C, 210 DEG C, 220 DEG C, 230 DEG C or 240 DEG C, outlet temperature is 120 DEG C, 130 DEG C, 140 DEG C, 150 DEG C, 160 DEG C, 170 DEG C
Or 180 DEG C, that is, obtain the Si-C composite material with carbon coating layer.
In a kind of optional embodiment, described carbonization treatment step, it is specially：
The Si-C composite material is placed in heater, 30~60min is first purified under protective atmosphere, then with 5
~10 DEG C/min heating rate is warming up to 800~1000 DEG C, after being incubated 1~3h, is cooled to room temperature, obtains silicon-carbon cathode material
Material.
In a kind of optional embodiment, the heater is in tube furnace, rotary furnace, batch-type furnace or roller kilns
It is a kind of；
Preferably, the protective atmosphere is one kind in nitrogen, helium, neon, argon gas, hydrogen or argon hydrogen gaseous mixture；
Preferably, the flow of the protective atmosphere is 40~60mL/min.
The purpose for carrying out carbonization treatment is to optimize the porous knot of composite for the intensity for the raising composite that improves
Structure, and then obtain porous honey comb like silicon-carbon cathode material；Effectively alleviate the bulk effect of silica-base material, improve following for material
Ring performance；And the structural stability and dynamic performance that obtained material has had.
In a detailed embodiment, optionally, carbonization treatment step is specially：(1) Si-C composite material is placed in
In tube furnace, rotary furnace, batch-type furnace or roller kilns, under the protective atmospheres such as nitrogen, helium, neon purify 30min, 40min,
50min or 60min；(2) with 5 DEG C/min, 6 DEG C/min, 7 DEG C/min, 8 DEG C/min, 9 DEG C/min or 10 DEG C/min heating rate
800 DEG C, 900 DEG C, 1000 DEG C or 1100 DEG C are warming up to, after being incubated 1h, 2h or 3h, is cooled to room temperature, and whole process is in protectiveness gas
Carried out under atmosphere, obtain silicon-carbon cathode material.
The mode for being cooled to room temperature is preferably to naturally cool to room temperature.
Second aspect, present embodiment provides a kind of silicon-carbon cathode material, by the system of above-described silicon-carbon cathode material
Preparation Method is made.
The third aspect, present embodiment provides a kind of lithium ion battery, including positive pole, negative pole, barrier film and electrolyte, described
Negative pole includes above-described silicon-carbon cathode material.
In present embodiment second aspect and the third aspect, lithium ion battery negative material, which removes, uses above-mentioned silicon-carbon cathode material
Material is used as beyond active material, and remaining composition and structure refer to prior art；Its system of positive pole, negative pole and lithium ion battery structure
Preparation Method refers to routine techniques, is added with differing only in lithium ion battery negative material for routine techniques by the
The silicon-carbon cathode material that the preparation method of silicon-carbon cathode material described in one side obtains.
The silicon-carbon cathode material that Pass through above-mentioned technical proposal is prepared, there is preferable chemical property, as lithium
Ion battery cathode material uses, and cost is low, stable performance, good conductivity, and specific capacity is high, has extended cycle life.
The lithium ion battery and silicon-carbon cathode material of the present invention, cost is low, stable performance, and specific capacity is high, good conductivity,
Have extended cycle life, electrochemical performance.Using silicon alloy as raw material, using above-mentioned technical proposal, the silicon-carbon cathode material prepared
The average grain diameter of material is 80~150nm, and first charge-discharge specific capacity at room temperature is about 900mAh/g, after 20 circulations,
Reversible specific capacity is about 720mAh/g.
With reference to specific embodiment, comparative example and accompanying drawing, the invention will be further described.
Embodiment 1
A kind of preparation method of silicon-carbon cathode material, comprises the following steps：
(a) pickling processes：Using silico-aluminum powder as raw material, the particle diameter of its silico-aluminum powder is 55 μm, silico-aluminum
The mass fraction of silicon is 13% in powder；Mass concentration is first used to carry out a pickling for 10% hydrochloric acid solution, the time is
20min；Aperture is used to be filtered for 1 μm of filter substrate again；Then rinsed using deionized water；Finally at 100 DEG C
Under conditions of be dried, and then eliminate the aluminium in silico-aluminum powder, and obtained porous silicon；
(b) carbon coating is handled：Obtained porous silicon is put into the glucose solution that mass concentration is 10%, its porous silicon
Mass ratio with glucose solution is 1：8, after stirring 60min, ultrasonic disperse 30min, then done under conditions of 180 DEG C
It is dry, form the Si-C composite material with carbon coating layer；
(c) carbonization treatment：Obtained Si-C composite material is placed in tube furnace, first purifies 30min in a nitrogen atmosphere,
900 DEG C are warming up to 8 DEG C/min heating rate again, after being incubated 2h, room temperature is cooled to, obtains silicon-carbon cathode material.
Embodiment 2
A kind of preparation method of silicon-carbon cathode material, comprises the following steps：
(a) pickling processes：Using silico-aluminum powder as raw material, the particle diameter of its silico-aluminum powder is 35 μm, silico-aluminum
The mass fraction of silicon is 10% in powder；Mass concentration is first used to carry out a pickling for 10% hydrochloric acid solution, the time is
30min；Aperture is used to be filtered for 2 μm of filter substrate again；Then rinsed using deionized water；Finally at 80 DEG C
Under the conditions of be dried, and then eliminate the aluminium in silico-aluminum powder, and obtained porous silicon；
(b) carbon coating is handled：Obtained porous silicon is put into the glucose solution that mass concentration is 10%, its porous silicon
Mass ratio with glucose solution is 1：10, after stirring 90min, ultrasonic disperse 60min, then done under conditions of 150 DEG C
It is dry, form the Si-C composite material with carbon coating layer；
(c) carbonization treatment：Obtained Si-C composite material is placed in tube furnace, first purifies 60min in a nitrogen atmosphere,
1000 DEG C are warming up to 10 DEG C/min heating rate again, after being incubated 1h, room temperature is cooled to, obtains silicon-carbon cathode material.
Embodiment 3
A kind of preparation method of silicon-carbon cathode material, comprises the following steps：
(a) pretreatment of raw material：Using silico-aluminum powder as raw material, the particle diameter of its silico-aluminum powder is 50 μm, and sial closes
The mass fraction of silicon is 12% in bronze end；Pulverization process is carried out to raw material by the way of air-flow crushing, admission pressure is
0.4Mpa, crushing pressure are 0.6Mpa, and the particle diameter of the powder obtained after crushing is 15 μm；
(b) pickling processes：Mass concentration is first used to carry out a pickling, time 20min for 10% hydrochloric acid solution；Again
Aperture is used to be filtered for 1 μm of filter substrate；Then rinsed using deionized water；Finally under conditions of 100 DEG C
It is dried in vacuo, and then eliminates the aluminium in silico-aluminum powder, and has obtained porous silicon；
(c) carbon coating is handled：Obtained porous silicon is put into the glucose solution that mass concentration is 10%, its porous silicon
Mass ratio with glucose solution is 1：8, at room temperature after magnetic agitation 70min, ultrasonic disperse 40min, then be spray-dried,
The pressure of spray drying is 0.2Mpa, and inlet temperature is 180 DEG C, and outlet temperature is 120 DEG C, forms the silicon-carbon with carbon coating layer
Composite；
(d) carbonization treatment：Obtained Si-C composite material is placed in tube furnace, first purifies 50min in a nitrogen atmosphere,
950 DEG C are warming up to 8 DEG C/min heating rate again, after being incubated 2h, room temperature is cooled to, whole nitrogen protection, obtains silicon-carbon and bear
Pole material.
Embodiment 4
A kind of preparation method of silicon-carbon cathode material, comprises the following steps：
(a) pretreatment of raw material：Using silico-aluminum powder as raw material, the particle diameter of its silico-aluminum powder is 70 μm, and sial closes
The mass fraction of silicon is 20% in bronze end；Pulverization process is carried out to raw material by the way of air-flow crushing, is first put into raw material
In hopper；Feed motor is opened again, and the rotating speed for adjusting twin-screw is 300rpm；Powder by twin-screw precomminution enters air-flow
Crushing chamber, it is 0.6Mpa to control admission pressure, and crushing pressure is 0.8Mpa；Powder after crushing passes through cyclone separator and trapping
Systematic collection；The particle diameter of the powder obtained after crushing is 8 μm.
Step (b), (c) and (d) it is same as Example 3.
Embodiment 5
A kind of preparation method of silicon-carbon cathode material, comprises the following steps：
(b) pickling processes：First the powder obtained by air-flow crushing is put into the hydrochloric acid solution that mass concentration is 20%,
Carry out a pickling, time 10min；Aperture is used to be filtered for 3 μm of filter substrate again；Then carried out using distilled water
Rinsing；It is finally putting into vacuum drying chamber and is dried, dry temperature is 90 DEG C, obtains porous silicon.
Step (a), (c) and (d) it is same as Example 3.
Embodiment 6
A kind of preparation method of silicon-carbon cathode material, comprises the following steps：
(b) pickling processes：First the powder obtained by air-flow crushing is put into the hydrochloric acid solution that mass concentration is 5%,
Carry out a pickling, time 60min；Aperture is used to be filtered for 0.5 μm of filter substrate again；Use again mass concentration for
10% hydrofluoric acid solution carries out white picking, time 10min；Then rinsed using distilled water；It is finally putting into vacuum
It is dried in drying box, dry temperature is 100 DEG C, obtains porous silicon.
Step (a), (c) and (d) it is same as Example 3.
Embodiment 7
A kind of preparation method of silicon-carbon cathode material, a pickling is secondary using sulfuric acid as different from Example 6
Using hydrofluoric acid and the mixed solution of hydrogen peroxide, remaining is same as Example 6 for pickling.
Embodiment 8
A kind of preparation method of silicon-carbon cathode material, comprises the following steps：
(c) carbon coating is handled：By obtained porous silicon be put into mass concentration be 8% sucrose solution in, its porous silicon and
The mass ratio of sucrose solution is 1：10, at room temperature after magnetic agitation 60min, ultrasonic disperse 60min, then be spray-dried, spray
The pressure that mist is dried is 0.2Mpa, and inlet temperature is 240 DEG C, and outlet temperature is 180 DEG C, forms the silicon-carbon with carbon coating layer and answers
Condensation material；
Step (a), (b) and (d) it is same as Example 3.
Embodiment 9
A kind of preparation method of silicon-carbon cathode material, carbon precursor is using starch as different from Example 8, remaining
It is same as Example 8.
Embodiment 10
A kind of preparation method of silicon-carbon cathode material, comprises the following steps：
(d) carbonization treatment：Obtained Si-C composite material is placed in rotary furnace, first purifies 30min under helium atmosphere,
800 DEG C are warming up to 5 DEG C/min heating rate again, after being incubated 3h, is cooled to room temperature, whole helium protection, the flow of helium
For 40mL/min, silicon-carbon cathode material is obtained.
Step (a), (b) and (c) it is same as Example 3.
Embodiment 11
A kind of preparation method of silicon-carbon cathode material, replaces with silicon magnesium by silico-aluminum powder as different from Example 3
Alloy powder, remaining is same as Example 3.
Embodiment 12
A kind of preparation method of silicon-carbon cathode material, replaces with ferrosilicon by silico-aluminum powder as different from Example 3
Alloy powder, remaining is same as Example 3.
Comparative example 1
A kind of preparation method of silicon-carbon cathode material, step (a) as different from Example 3, remaining step with implementation
Example 3 is identical.
(a) pretreatment of raw material：Silico-aluminum powder stock is pre-processed by the way of ball milling.
Comparative example 2
A kind of preparation method of silicon-carbon cathode material, step (b) as different from Example 3, remaining step with implementation
Example 3 is identical.
(b) pickling processes：Acid attack 20min is carried out using hydrofluoric acid solution, then washed with water, at 100 DEG C
Under the conditions of carry out in drying, obtain porous silicon.
Comparative example 3
A kind of preparation method of silicon-carbon cathode material, step (c) as different from Example 3, remaining step with implementation
Example 3 is identical.
(c) carbon coating is handled：By porous silicon and 10% glucose solution using mass ratio as 1：5 mix 30min, then
Vacuum drying, form the Si-C composite material with carbon coating layer.
Comparative example 4
A kind of preparation method of silicon-carbon cathode material, step (d) as different from Example 3, remaining step with implementation
Example 3 is identical.
(d) carbonization treatment：In an inert atmosphere, it is 1050 DEG C in carburizing temperature, under conditions of carbonization time is 0.5h, enters
Row carbonization treatment.
Comparative example 5
A kind of preparation method of silicon-carbon cathode material, catalyst inducement is used as using argent using of the prior art
The method that the method for chemical attack prepares carbon-silicon composite material.
The silicon-carbon cathode material that each embodiment and comparative example are prepared carries out SEM sweep tests.Wherein, only with implementation
It is described in detail exemplified by example 3.Fig. 1 (a) and (b) respectively illustrate the porous silicon and carbonization that pickling processes obtain in embodiment 3
Handle the SEM figures of obtained silicon-carbon cathode material.As can be seen from Figure 1 silico-aluminum powder stock is after pickling processes,
Porous silicon is obtained, and its surface topography is preferable；After porous silicon is further across carbon coating and carbonization treatment, honeycomb has been obtained
The silicon-carbon cathode material of shape structure, the structure can effectively alleviate the volumetric expansion in charge and discharge process, so as to alleviate electric work
The phenomenon of property material powder of detached, improve the cyclical stability of material.
Electrochemical property test
Silicon-carbon cathode material made from embodiment 1-12 and comparative example 1-5 is made into half-cell respectively, and tests its phase
Powered-down chemical property, test result are as shown in table 1.Wherein, prepared by half-cell：Using active material as positive pole, lithium piece is negative pole group
Button cell is dressed up, conductive agent uses conductive carbon Super " p ", and barrier film celgard2400, electrolyte is from 1mol/L's
LiPF6Conducting salt and DMC：DEC：EC (wt%)=1：1：1 solvent.Test condition is：Discharge and recharge blanking voltage be 0.05~
Test reversible specific capacity first under 2V, 0.1C state, test loop efficiency 20 times under 0.2C, test result is as shown in table 1.
The electrochemical property test result of table 1
As can be seen from Table 1, reversible specific capacity is high first for silicon-carbon cathode material provided by the invention, has extended cycle life, surely
It is qualitative good；The chemical property of silicon-carbon cathode material made from 1-12 of the embodiment of the present invention is substantially due to comparative example 1-5.Specifically
Say, the preparation method of silicon-carbon cathode material provided by the invention, not only better than the preparation method of existing silicon-carbon cathode material,
And the pretreatment of raw material limited in the present invention and pickling processes mode of operation, and carbon coating processing and the operation of carbonization treatment
In mode and range of operating parameters, obtained silicon-carbon cathode material, there is more excellent chemical property, specific capacity is higher,
Cyclical stability is more preferable.
In addition, Fig. 2 shows cycle-index-specific discharge capacity figure of silicon-carbon cathode material in embodiment 3.From Fig. 2
Can further it find out, the electrochemistry such as the reversible specific capacity of the silicon-carbon cathode material obtained by embodiment 3 and cycle efficieny
Index is in higher level.It should be noted that what the preparation method of the silicon-carbon cathode material described in remaining embodiment obtained
The cycle performance spectrogram of silicon-carbon cathode material is substantially similar to Fig. 2.Thus illustrate, the system of silicon-carbon cathode material provided by the invention
The silicon-carbon cathode material that Preparation Method obtains improves the cycle performance of lithium ion battery, has on lithium ion battery and well should
Use prospect.
Finally it should be noted that：Various embodiments above is merely illustrative of the technical solution of the present invention, rather than its limitations；To the greatest extent
The present invention is described in detail with reference to foregoing embodiments for pipe, it will be understood by those within the art that：Its according to
The technical scheme described in foregoing embodiments can so be modified, either which part or all technical characteristic are entered
Row equivalent substitution；And these modifications or replacement, the essence of appropriate technical solution is departed from various embodiments of the present invention technology
The scope of scheme.
Claims (10)
1. a kind of preparation method of silicon-carbon cathode material, it is characterised in that comprise the following steps：
Using silicon alloy powder as raw material, through pickling processes, after removing remaining metal in silicon alloy powder in addition to silicon, obtain more
Hole silicon；
The porous silicon is put into carbon precursor, carries out carbon coating processing, forms the Si-C composite material with carbon coating layer；
The Si-C composite material is subjected to carbonization treatment, obtains silicon-carbon cathode material.
2. the preparation method of silicon-carbon cathode material according to claim 1, it is characterised in that the silicon alloy closes for sial
One kind or at least two combination in gold, Antaciron, Si-Mg alloy, silicon copper, silicon nickel alloy and silicomangan, preferably
For one kind in silico-aluminum, Antaciron and Si-Mg alloy or at least two combination, more preferably silico-aluminum；
Preferably, the particle size range of the silicon alloy powder be 20~70 μm, preferably 30~60 μm, more preferably 35~
55μm；
Preferably, the mass fraction of silicon is 5%~20%, preferably 8%~15% in the silicon alloy powder, further preferably
For 10%~13%.
3. the preparation method of silicon-carbon cathode material according to claim 1, it is characterised in that before through pickling processes,
Also include the pulverization process step to raw material；
Preferably, pulverization process is carried out to raw material by the way of air-flow crushing；
Preferably, carry out first carrying out precomminution before air-flow crushing, the rotating speed of precomminution is 200~300rpm；
Preferably, the admission pressure of air-flow crushing is 0.4~0.6Mpa, and the pressure of crushing is 0.6~0.8Mpa；
Preferably, the particle size range of the powder obtained after air-flow crushing is 8~15 μm.
4. the preparation method of silicon-carbon cathode material according to claim 1, it is characterised in that described pickling processes include
Pickling, filtering and rinsing；
Preferably, the pickling processes include a pickling, filtering, white picking and rinsing；
Preferably, a pickling is using hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid and the acetic acid that mass concentration is 2%~20%
In solution it is a kind of or at least two combination, the time of a pickling is 10~60min；
Preferably, in the filtration step, the pore diameter range of filter substrate is 0.5~3 μm；
Preferably, the white picking is using hydrofluoric acid solution, hydrofluoric acid and the hydrogen peroxide that mass concentration is 3%~20%
Mixed solution or the mixed solution of hydrofluoric acid and nitric acid in one kind, the time of white picking is 5~30min；
Preferably, the rinsing is using deionized water, pure water or distilled water；
Preferably, dry step is also included after the rinse step, dry temperature is preferably 80~100 DEG C.
5. the preparation method of silicon-carbon cathode material according to claim 1, it is characterised in that the carbon precursor includes poly-
Vinyl alcohol, polyvinyl chloride, butadiene-styrene rubber breast, polymethyl methacrylate, polyacrylonitrile, phenolic resin, pitch, glucose, sugarcane
In sugar, cellulose, epoxy resin and starch any one or at least two combination.
6. the preparation method of the silicon-carbon cathode material according to any one of Claims 1 to 5, it is characterised in that described carbon
Cladding processing comprises the following steps：
By the porous silicon and carbon precursor according to 1：6~10 mass ratio mixing, after stirring 60~90min, ultrasonic disperse
30~60min, then be dried, obtain the Si-C composite material with carbon coating layer；
Preferably, using magnetic agitation, the temperature of stirring is 20~30 DEG C for the stirring；
Preferably, the drying is using spray drying, and the pressure of spray drying is 0.2~0.4Mpa, inlet temperature 180
~240 DEG C, outlet temperature is 120~180 DEG C.
7. the preparation method of the silicon-carbon cathode material according to any one of Claims 1 to 5, it is characterised in that described carbon
Change processing comprises the following steps：
The Si-C composite material is placed in heater, 30~60min is first purified under protective atmosphere, then with 5~10
DEG C/min heating rate is warming up to 800~1000 DEG C, after being incubated 1~3h, room temperature is cooled to, obtains silicon-carbon cathode material.
8. the preparation method of silicon-carbon cathode material according to claim 7, it is characterised in that the heater is tubular type
One kind in stove, rotary furnace, batch-type furnace or roller kilns；
Preferably, the protective atmosphere is one kind in nitrogen, helium, neon, argon gas, hydrogen or argon hydrogen gaseous mixture；
Preferably, the flow of the protective atmosphere is 40~60mL/min.
9. a kind of silicon-carbon cathode material, it is characterised in that as the system of the silicon-carbon cathode material described in any one of claim 1~8
Preparation Method is made.
10. a kind of lithium ion battery, including negative pole, it is characterised in that the negative pole includes the silicon-carbon cathode described in claim 9
Material.
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| CN112885998A (en) * | 2021-01-20 | 2021-06-01 | 惠州市豪鹏科技有限公司 | Silicon composite material and preparation method thereof, negative plate and lithium ion battery |
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| CN113178552A (en) * | 2021-03-26 | 2021-07-27 | 四川大学 | High-tap-density porous silicon-carbon composite material, preparation method thereof and application of negative electrode of lithium ion battery |
| CN113178552B (en) * | 2021-03-26 | 2023-03-10 | 四川大学 | High-tap-density porous silicon-carbon composite material, preparation method thereof and application of negative electrode of lithium ion battery |
| CN114094090A (en) * | 2021-11-10 | 2022-02-25 | 中汽创智科技有限公司 | Silicon-based negative electrode material and preparation method and application thereof |
| CN114094090B (en) * | 2021-11-10 | 2023-12-22 | 中汽创智科技有限公司 | Silicon-based anode material and preparation method and application thereof |
| CN114583122A (en) * | 2022-01-30 | 2022-06-03 | 合肥国轩高科动力能源有限公司 | Carbon-silicon negative electrode material, preparation method thereof and lithium ion battery |
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