CN110474032A - It is a kind of to be given up the silicon-carbon cathode material and preparation method thereof of silicon based on photovoltaic - Google Patents
It is a kind of to be given up the silicon-carbon cathode material and preparation method thereof of silicon based on photovoltaic Download PDFInfo
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Abstract
It is given up the silicon-carbon cathode material and preparation method thereof of silicon the present invention provides a kind of based on photovoltaic.The preparation method comprises the following steps: (1) crushing the useless silicon material of collection, is dried to obtain waste silicon powder；(2) waste silicon powder is placed in progress high temperature removal of impurities in inert atmosphere, obtains high-purity silicon powder after overpickling purifying and drying；(3) high-purity silicon powder is added in decentralized medium, obtains nano-silicon solution through high speed ball milling；(4) the nano-silicon solution is collected and is adjusted and contained admittedly, sand milling is uniformly mixed after organic carbon source, conductive agent and dispersing agent are added according to a certain percentage；(5) mixed solution is sprayed dry and calcined, finally obtain silicon-carbon cathode material.The effect of silicon-carbon cathode material head prepared by this method is high, good cycling stability, preparation method have cost advantage, it is easy to operate, be suitble to industrialization production.
Description
Technical field
The present invention relates to battery material fields, and in particular to it is a kind of based on photovoltaic give up silicon silicon-carbon cathode material and its preparation
Method.
Background technique
With the high speed development of mobile electronic product and new-energy automobile industry, energy of the one side market to lithium ion battery
The requirement of metric density is also increasingly increasing, and another aspect national policy also in the development for carrying forward vigorously high energy density cells, " promotees
Into automobile power cell developing activity scheme (2017) " clearly propose, the monomer specific energy of the year two thousand twenty lithium-ion-power cell is wanted
More than 300 Wh/kg.As the critical material of lithium ion battery, the selection of negative electrode material plays decision to the performance of the energy content of battery
The effect of property.The theoretical specific capacity of traditional negative electrode material graphite only has 372 mAh/g, be no longer satisfied high-energy density lithium from
The requirement of sub- battery.And the theoretical capacity of silicon is up to 4200 mAh/g, is ten times of graphite theoretical capacity or more.To reach
The target of 300 Wh/kg, the material system that silicon-based anode matches nickelic anode has been common recognition in industry.
Although silicon based anode material has broad application prospects, there are still skills in actual use for silicon materials
Art barrier needs to break through, wherein main problem has: 1) volume expansion reaches 320% after embedding lithium, and volume expansion can further be led
Cause the continuous formation of material dusting, electrode structure variation and solid electrolyte (SEI) film；2) intrinsic to belong to semiconductor material, it leads
It is electrically poor.Due to the limitation of above-mentioned bottleneck problem, silicon materials even cannot be used individually as negative electrode material, current battery material
Expect that enterprise's Main is to be used in conjunction with silicon and graphite, conductive agent and other carbon materials, the introducing of carbon material can
To improve the electric conductivity of silicon-carbon cathode.For the volume expansion problem of silicon, nanosizing is a kind of effective solution method.Study table
It is bright, when size less than 150 nm can effectively alleviate volume expansion problem to silicon materials at least one dimension, prevent material
Feed powderization is broken.
Currently, LITHIUM BATTERY nano silica fume mostly uses plasma method and laser method to prepare in the market, SiH is mainly utilized4
Gas is that reaction raw materials are prepared by being vapor-deposited, although the nano silica fume purity of such method preparation is higher, size tunable,
But high production cost, the serious development for restricting downstream silicon carbon material industry.In recent years, photovoltaic industry is fast-developing, and 2018
Global polysilicon yield reaches 43.0 ten thousand tons, and wherein yield accounting in China's is more than 50%.During solar silicon wafers processing,
The high-purity crystal silicon that purity reaches 99.9999% can be cut into certain size and shape, in the process about 40% it is high-purity
The submicron order waste material that crystalline silicon can become discarded silico briquette and be blended in cutting fluid, therefore China has more than 100,000 tons every year
It cuts useless silicon to generate, wherein the useless silicon material of the submicron order of accounting about 50% for photovoltaic industry because being difficult to be discarded due to recycling.
The submicron order generated in photovoltaic industry cutting process is prepared LITHIUM BATTERY nano-silicon after purification and refinement not only can be real
Existing resource utilization recycles, and can substantially reduce the production cost of nano-silicon, promote silicon-carbon cathode material and lithium ion
The development of battery industry.
Chinese patent CN104112850 provides a kind of lithium ion battery negative material based on photovoltaic industry scrap silicon
Purifying and modified micron or submicron order silicon are simply mixed preparation method with graphite, and with particular adhesive system
It applies after matching in lithium ion battery negative material.Silicon is used in mixed way with graphite can alleviate to a certain extent silicon volume it is swollen
It is swollen, improve the electric conductivity of composite material, but as lithium ion battery negative material in use, the partial size of silicon is not closed
The control of reason, there are still biggish volume expansions for micron-sized silicon, at the same the silicon not coated can directly and electrolyte contacts, with
The growth electrolyte of SEI film can constantly be consumed.Chinese patent CN104701491 is starched with the useless silicon in silicon wafer production process
Material is raw material, prepares nano-silicon porous silicon into excessively dry, pickling, ball milling and strong acid corrosion, and directly as lithium-ion electric
Pond negative electrode material uses.Nano-silicon porous silicon can alleviate the volume expansion of silicon to a certain extent, but big used by it
Amount strong acid corrosion the preparation method can cause environmental pollution and be not suitable for large-scale production.
Summary of the invention
In view of the above technical problems, the invention proposes it is a kind of based on photovoltaic give up silicon silicon-carbon cathode material and its preparation side
Method significantly reduces production cost as raw material using the useless silicon mud of photovoltaic industry, and preparation process is simple, is suitble to industrialization
Amplification.It is refined using substep, in the reasonable scope by the size controlling of silicon powder, partial size and specific surface area is balanced, to make to receive
Rice silicon can play more preferably performance.In addition, organic carbon source is introduced in sand grinding process, it can be in silicon materials through high-temperature calcination
Surface forms stable, uniform agraphitic carbon clad, prevents silicon materials and electrolyte from directly contacting, advantageously forms stable
SEI film improves the coulombic efficiency and cyclical stability of material.
In order to solve the above technical problems, the technical scheme is that
A kind of to be given up the silicon-carbon cathode material of silicon based on photovoltaic, the silicon-carbon cathode material is spherical silicon-carbon composite cathode material
Material, the agraphitic carbon that organic matter pyrolysis is formed are coated on the surface layer of flake nano silicon, internal flake nano silicon by after coating and
Conductive agent is constituted；The flake nano silicon is that the leftover pieces generated by photovoltaic industry when cutting crystal silicon chip are obtained by processing
, the partial size of flake nano silicon is 50 ~ 200 nm, with a thickness of 10 ~ 50nm；The quality accounting of each component is respectively as follows: flake nano
Silicon 50% ~ 90%, conductive agent 5 ~ 20%, organic cracking carbon 10 ~ 30%.
It is described based on photovoltaic give up silicon silicon-carbon cathode material preparation method, comprising the following steps:
(1) by photovoltaic give up silicon material crush, it is dry after obtain waste silicon powder, waste silicon powder is placed in progress high temperature removal of impurities in inert atmosphere,
Then high-purity silicon powder is obtained after overpickling and drying；
(2) high-purity silicon powder and zirconia ball are added in solvent by a certain percentage, are obtained after high speed ball milling in an inert atmosphere
Nano-silicon suspension；
(3) solid content is collected and adjusted to the nano-silicon suspension, organic carbon source, conductive agent and dispersing agent is added, then carries out
Sealing, which is sanded, to be uniformly mixed, and mixed slurry is obtained；
(4) mixed slurry is spray-dried and is calcined in an inert atmosphere, finally obtain silicon-carbon cathode material.
Further, the useless silicon material generated when the useless silicon of photovoltaic is Buddha's warrior attendant wire cutting solar energy crystal silicon chip in the step (1),
Wherein the purity of sliced crystal silicon is greater than 99.9999% or more, and the silicone content for silicon material of giving up is greater than 80%.
Further, it carries out high-temperature calcination first in the step (1) to remove most of organic impurities, then carries out pickling；
Pickling is purified including pickling twice, is carried out pickling with the mixing of one or more of dilute hydrochloric acid, dust technology and dilute sulfuric acid first, is passed through
Second of pickling is carried out with hydrofluoric acid again after over cleaning, the temperature of the pickling is 20 ~ 95 DEG C, and pickling time is 0.5 ~ 24 h.
Further, when step (2) the high speed ball milling, solvent be deionized water, ethyl alcohol, butanol, methanol, isopropanol,
One of cyclohexanone, acetone, butanone or hexamethylene are a variety of, and solid content is 5 ~ 50%.
Further, when step (2) the high speed ball milling, the mass ratio of high-purity silicon powder and zirconia ball is 10:(5 ~ 30),
The partial size of zirconium oxide is 0.1 ~ 3 mm, ball milling speed 100-800rpm.
Further, the organic carbon source in the step (3) be phenolic resin, epoxy resin, sucrose, starch, chitosan or
One of glucose is a variety of.
Further, the dispersing agent in the step (3) is polyvinylpyrrolidone, polyethyleneimine, carboxymethyl cellulose
One of sodium or neopelex are a variety of.
Further, solid content is 5 ~ 50% when being sanded in the step (3), is sanded 1000 ~ 3000 rpm of speed, when sand milling
Between 0.5 ~ 10 h.
Further, calcining is the material after being spray-dried with the heating rate liter of 1 ~ 20 DEG C/min in the step (4)
For temperature to 600 ~ 1000 DEG C of 1 ~ 4h of heat preservation, inert atmosphere is one or more of nitrogen, argon gas or hydrogen.
The beneficial effects of the present invention are:
(1) present invention gives up silicon as raw material using photovoltaic, the waste silicon powder process being mixed in cutting fluid generated when cutting silicon wafer is purified,
Silicon-carbon cathode material is used to prepare after obtaining after refinement, it can be achieved that the recycling of useless silicon recycles, and is conducive to the hair of circular economy
Exhibition.
(2) silicon-carbon cathode material prepared by the present invention has explicit costs advantage.Prepared by plasma method and laser method
Nano-silicon selling at exorbitant prices, cost account for about the 50% of silicon carbon material overall cost.The present invention handles useless silicon by simple process
Nano-silicon solution can be obtained, therefore can greatly reduce cost.Nano-solution and a certain proportion of organic carbon source and conductive agent are mixed
It can be obtained silicon-carbon cathode material through drying and calcination after conjunction, centre omits the step that nano-silicon solution is dry, simplifies work
Skill process, while also further reduced production cost.
(3) wet ball grinding process for refining proposed by the present invention can be final to obtain by the size controlling of silicon powder in the reasonable scope
To the flake nano silicon of uniform particle sizes, this technique can keep lower specific surface area while refining silicon powder partial size,
Therefore prepared flake nano silicon can play its chemical property to greatest extent.
(4) the invention proposes the near-spherical silicon-carbon cathode materials that a kind of surface is uniformly coated by agraphitic carbon.It is being sanded
Organic carbon source and conductive agent are introduced in the process, and agraphitic carbon can be evenly coated at flake nano silicon face, nothing after calcined material
Amorphous carbon layer can effectively prevent silicon materials and electrolyte directly to contact, and advantageously form stable SEI film, improve the stabilization of material
Property；The addition of another aspect carbon material and conductive agent can improve the electric conductivity of material entirety, improve the chemical property of material.
Detailed description of the invention
Fig. 1 is the SEM figure for the silicon-carbon cathode material that the present invention obtains.
Fig. 2 is the cyclical stability figure for the silicon-carbon cathode material that the present invention obtains.
Specific embodiment
The present invention is further described with case study on implementation below, but the present invention is not limited solely to following implementation
Example.
Experimental drug and method in the following example, use according to normal conditions or according to product manual.
The prepared silicon-carbon cathode material of invention is assembled into half-cell and carries out electrochemical property test: silicon-carbon cathode material
Material: Super P: binder is homogenized according to the mass ratio of 8:1:1, smear.Wherein, binder are as follows: sodium carboxymethylcellulose
(CMC): butadiene-styrene rubber (SBR): polyacrylic acid (PAA) mass ratio is the solution of 1:1:1, electrolyte LiPF6Conventional electrolysis liquid.
Lithium piece is used as to electrode, is assembled into CR2025 button cell.Under normal temperature condition, LANHE CT2001A indigo plant electrical measurement test system is utilized
Charge-discharge test is carried out under the current density of 100 mA/g, voltage range is 0.005 ~ 2.0 V.
Embodiment 1
The present embodiment based on photovoltaic give up silicon silicon-carbon cathode material preparation method, steps are as follows:
(1) photovoltaic waste silicon powder is broken to average grain diameter less than 2 mm using pulverizer, place then is dried in air dry oven
Reason is to moisture less than 2%.Waste silicon powder after drying is placed in horizontal pipe furnace, is heated in a nitrogen atmosphere with the speed of 5 DEG C/min
High temperature removal of impurities is carried out to 900 DEG C of 2 h of heat preservation.
(2) silicon material after high temperature cleaning is immersed in the dilute hydrochloric acid of 1 M, is filtered after 40 DEG C of stirring 4h, is used deionized water
It cleans to neutrality.Then second of pickling is carried out, the silicon material after cleaning is immersed in the hydrofluoric acid solution of 1 M, is stirred at room temperature 2
It filters after h, cleaned with deionized water to neutrality again.Then purity is obtained after the silicon powder after cleaning being dried in a vacuum to be greater than
99.5% high-purity silicon powder.
(3) 50 g high-purity silicon powders are weighed and 150g zirconium oxide bead is added in 75 g dehydrated alcohols, under 300 rpm speed
Nano-silicon solution is obtained after ball milling 5h.Dehydrated alcohol is added into nano-silicon solution by solid containing adjusting to 20%, then weighs 300
G nano-silicon solution obtains mixed slurry after being separately added into 30 g phenolic resin, 10 g graphenes and 20 g polyethyleneimines.It will
Mixed slurry pours into sand mill, and 3 h are sanded under the conditions of 2000 rpm.Then the slurry after sand milling is spray-dried,
It is calcined under nitrogen atmosphere after drying, 900 DEG C of 2 h of heat preservation is warming up to the rate of 5 DEG C/min, finally obtaining microscopic appearance is class
Spherical silicon-carbon cathode material.
Embodiment 2
The present embodiment based on photovoltaic give up silicon silicon-carbon cathode material preparation method, steps are as follows:
(1) photovoltaic waste silicon powder is broken to average grain diameter less than 2 mm using pulverizer, place then is dried in vacuum oven
Reason is to moisture less than 2%.Waste silicon powder after drying is placed in horizontal pipe furnace, is heated in a nitrogen atmosphere with the speed of 5 DEG C/min
High temperature removal of impurities is carried out to 700 DEG C of 2 h of heat preservation.
(2) silicon material after high temperature cleaning is immersed in the dust technology of 1 M, is centrifuged after 70 DEG C of 5 h of stirring, is used deionized water
It is cleaned repeatedly to neutrality.Then second of pickling is carried out, the silicon material after cleaning is immersed in the hydrofluoric acid solution of 0.5 M, room
It is centrifuged after temperature stirring 10h, cleaned with deionized water to neutrality again.Then it is obtained after the silicon powder after cleaning being dried in a vacuum pure
Degree is greater than 99.5% high-purity silicon powder.
(3) 50 g high-purity silicon powders are weighed and 80 g zirconium oxide beads are added in 80 g deionized waters, under 400 rpm speed
Nano-silicon solution is obtained after 3 h of ball milling.Deionized water is added into nanometer silicon suspension by solid containing adjusting to 20%, then weighs
300 g nano-silicon solution obtain mixing slurry after being separately added into 35 g glucose, 10 g graphenes and 20 g polyvinylpyrrolidones
Material.Mixed slurry is poured into sand mill, 2 h are sanded under the conditions of 2500 rpm.Then the slurry after sand milling is sprayed
It is dry, it is calcined under argon atmosphere after dry, 700 DEG C of 2 h of heat preservation is warming up to the rate of 5 DEG C/min, finally obtain microcosmic shape
Looks are the silicon-carbon cathode material of near-spherical.
Embodiment 3
The present embodiment based on photovoltaic give up silicon silicon-carbon cathode material preparation method, steps are as follows:
(1) photovoltaic waste silicon powder is broken to average grain diameter less than 2 mm using pulverizer, place then is dried in air dry oven
Reason is to moisture less than 2%.Waste silicon powder after drying is placed in horizontal pipe furnace, is heated in a nitrogen atmosphere with the speed of 5 DEG C/min
High temperature removal of impurities is carried out to 700 DEG C of 2 h of heat preservation.
(2) silicon material after high temperature cleaning is immersed in the dilute sulfuric acid of 2 M, is centrifuged after 60 DEG C of 5 h of stirring, is used deionized water
It is cleaned repeatedly to neutrality.Then second of pickling is carried out, the silicon material after cleaning is immersed in the hydrofluoric acid solution of 1 M, room temperature
It is centrifuged after stirring 5h, cleaned with deionized water to neutrality again.Then the silicon powder after cleaning is obtained after drying in air dry oven
It is greater than 99.5% high-purity silicon powder to purity.
(3) 50 g high-purity silicon powders are weighed and 150 g zirconium oxide beads are added in 50 g acetone, the ball under 400 rpm speed
Nano-silicon solution is obtained after grinding 3 h.Acetone is added into nanometer silicon suspension by solid containing adjusting to 50%, then weighs 200 g and receives
Rice silicon solution is separately added into the sodium carboxymethylcellulose that 50 g epoxy resin, 10 g carbon nanotubes and 40 g mass fractions are 30%
Mixed slurry is obtained after aqueous solution.Mixed slurry is poured into sand mill, 1 h is sanded under the conditions of 3000 rpm.Then by sand
Slurry after mill is spray-dried, and is calcined under hydrogen atmosphere after dry, is warming up to 900 DEG C of heat preservations 2 with the rate of 5 DEG C/min
H finally obtains the silicon-carbon cathode material that microscopic appearance is near-spherical.
Embodiment 4
The present embodiment based on photovoltaic give up silicon silicon-carbon cathode material preparation method, steps are as follows:
(1) photovoltaic waste silicon powder is broken to average grain diameter less than 2 mm using pulverizer, place then is dried in air dry oven
Reason is to moisture less than 2%.Waste silicon powder after drying is placed in horizontal pipe furnace, is heated in a nitrogen atmosphere with the speed of 5 DEG C/min
High temperature removal of impurities is carried out to 900 DEG C of 2 h of heat preservation.
(2) silicon material after high temperature cleaning is immersed in the dilute sulfuric acid and alkene hydrochloric acid mixed solution of 2 M, 70 DEG C of 5 h of stirring
It filters, cleaned repeatedly with deionized water to neutrality afterwards.Then second of pickling is carried out, the silicon material after cleaning is immersed in 1 M's
In hydrofluoric acid solution, it is stirred at room temperature after 4h and is centrifuged, is cleaned with deionized water to neutrality again.Then by the silicon powder after cleaning in air blast
The high-purity silicon powder that purity is greater than 99.5% is obtained in drying box after drying.
(3) 50 g high-purity silicon powders are weighed and 120 g zirconium oxide beads are added to 50 g methanol, the ball milling 2 under 500 rpm speed
Nano-silicon solution is obtained after h.Then 200 g nano-silicon solution are weighed, 50 g sucrose, 5 g carbon nanotubes, 5 g stones are separately added into
Mixed slurry is obtained after the aqueous povidone solution that black alkene and 40 g mass fractions are 30%.Mixed slurry is poured into sand
In grinding machine, 2 h are sanded under the conditions of 2500 rpm.Then the slurry after sand milling is spray-dried, in argon gas gas after drying
It is calcined under atmosphere, 900 DEG C of 2 h of heat preservation is warming up to the rate of 5 DEG C/min, finally obtain the silicon-carbon cathode that microscopic appearance is near-spherical
Material.
Embodiment 5
The present embodiment based on photovoltaic give up silicon silicon-carbon cathode material preparation method, steps are as follows:
(1) photovoltaic waste silicon powder is broken to average grain diameter less than 2 mm using pulverizer, place then is dried in air dry oven
Reason is to moisture less than 2%.Waste silicon powder after drying is placed in horizontal pipe furnace, is heated in a nitrogen atmosphere with the speed of 5 DEG C/min
High temperature removal of impurities is carried out to 900 DEG C of 2 h of heat preservation.
(2) silicon material after high temperature cleaning is immersed in the dust technology and alkene hydrochloric acid mixed solution of 2 M, 50 DEG C of 5 h of stirring
It is centrifuged, cleaned repeatedly with deionized water to neutrality afterwards.Then second of pickling is carried out, the silicon material after cleaning is immersed in 1 M's
In hydrofluoric acid solution, it is stirred at room temperature after 4 h and refilters, cleaned with deionized water to neutrality.Then by the silicon powder after cleaning dry
The high-purity silicon powder that purity is greater than 99.5% is obtained in dry case after drying.
(3) 50 g high-purity silicon powders are weighed and 100 g zirconium oxide beads are added in 80 g ethyl alcohol and deionized water mixed solution,
Nano-silicon solution is obtained after 2 h of ball milling under 500 rpm speed.Be added into nano-silicon solution deionized water will it is solid containing adjust to
30%, 200 g nano-silicon suspensions are then weighed, 50 g sucrose, 10 g carbon nanotubes, 20 g polyvinylpyrrolidines are separately added into
Mixed slurry is obtained after ketone and 20 g sodium carboxymethylcelluloses.Mixed slurry is poured into sand mill, under the conditions of 3000 rpm
2.5 h are sanded.Then the slurry after sand milling is spray-dried, is calcined under nitrogen atmosphere after dry, with the speed of 5 DEG C/min
Rate is warming up to 850 DEG C of 2 h of heat preservation, finally obtains the silicon-carbon cathode material that microscopic appearance is near-spherical.
Embodiment 6
The present embodiment based on photovoltaic give up silicon silicon-carbon cathode material preparation method, steps are as follows:
(1) photovoltaic waste silicon powder is broken to average grain diameter less than 2 mm using pulverizer, place then is dried in air dry oven
Reason is to moisture less than 2%.Waste silicon powder after drying is placed in horizontal pipe furnace, is heated in a nitrogen atmosphere with the speed of 5 DEG C/min
High temperature removal of impurities is carried out to 850 DEG C of 2 h of heat preservation.
(2) silicon material after high temperature cleaning is immersed in the dust technology and alkene sulfuric acid mixed solution of 2 M, and 10 h are stirred at room temperature
It filters, cleaned repeatedly with deionized water to neutrality afterwards.Then second of pickling is carried out, the silicon material after cleaning is immersed in 0.5 M
Hydrofluoric acid solution in, be stirred at room temperature after 12h and be centrifuged, cleaned with deionized water to neutrality again.Then the silicon powder after cleaning is existed
The high-purity silicon powder that purity is greater than 99.5% is obtained in drying box after drying.
(3) 50 g high-purity silicon powders are weighed and 150 g zirconium oxide beads are added in 80 g acetone, the ball under 450 rpm speed
Nano-silicon solution is obtained after grinding 2.5 h.Deionized water is added into nano-silicon solution by solid containing adjusting to 10%, then weighs 600
G nano-silicon suspension is separately added into 50 g glucose, 10 g carbon nanotubes, 20 g polyethyleneimines and 20 g carboxymethyl celluloses
Mixed slurry is obtained after plain sodium.Mixed slurry is poured into sand mill, 8 h are sanded under the conditions of 1500 rpm.Then it will be sanded
Slurry afterwards is spray-dried, and is calcined under nitrogen atmosphere after dry, is warming up to 650 DEG C of heat preservations 2 with the rate of 5 DEG C/min
H finally obtains the silicon-carbon cathode material that microscopic appearance is near-spherical.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent substitution, improvement and etc. done be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of given up the silicon-carbon cathode material of silicon based on photovoltaic, it is characterised in that: the silicon-carbon cathode material is spherical silicon
Carbon compound cathode materials, the agraphitic carbon that organic matter pyrolysis is formed is coated on the surface layer of flake nano silicon, after inside is by coating
Flake nano silicon and conductive agent are constituted；The flake nano silicon is the leftover pieces generated by photovoltaic industry when cutting crystal silicon chip
It is obtained by processing, the partial size of flake nano silicon is 50 ~ 200 nm, with a thickness of 10 ~ 50nm；The quality accounting of each component is distinguished
Are as follows: flake nano silicon 50% ~ 90%, conductive agent 5 ~ 20%, organic cracking carbon 10 ~ 30%.
2. it is according to claim 1 based on photovoltaic give up silicon silicon-carbon cathode material preparation method, it is characterised in that including
Following steps:
(1) by photovoltaic give up silicon material crush, it is dry after obtain waste silicon powder, waste silicon powder is placed in progress high temperature removal of impurities in inert atmosphere,
Then high-purity silicon powder is obtained after overpickling and drying；
(2) high-purity silicon powder and zirconia ball are added in solvent by a certain percentage, are obtained after high speed ball milling in an inert atmosphere
Nano-silicon suspension；
(3) solid content is collected and adjusted to the nano-silicon suspension, organic carbon source, conductive agent and dispersing agent is added, then carries out
Sealing, which is sanded, to be uniformly mixed, and mixed slurry is obtained；
(4) mixed slurry is spray-dried and is calcined in an inert atmosphere, finally obtain silicon-carbon cathode material.
3. according to claim 2 given up the silicon-carbon cathode material and preparation method thereof of silicon based on photovoltaic, it is characterised in that: institute
It states photovoltaic in step (1) to give up the useless silicon material generated when silicon is Buddha's warrior attendant wire cutting solar energy crystal silicon chip, wherein sliced crystal silicon
Purity is greater than 99.9999% or more, and the silicone content for silicon material of giving up is greater than 80%.
4. according to claim 2 given up the silicon-carbon cathode material and preparation method thereof of silicon based on photovoltaic, it is characterised in that: institute
It states and carries out high-temperature calcination in step (1) first to remove most of organic impurities, then carry out pickling；Pickling includes that pickling twice is pure
Change, carries out pickling with the mixing of one or more of dilute hydrochloric acid, dust technology and dilute sulfuric acid first, use hydrofluoric acid again after over cleaning
Second of pickling is carried out, the temperature of the pickling is 20 ~ 95 DEG C, and pickling time is 0.5 ~ 24 h.
5. according to claim 2 given up the silicon-carbon cathode material and preparation method thereof of silicon based on photovoltaic, it is characterised in that: institute
When stating step (2) high speed ball milling, solvent be deionized water, ethyl alcohol, butanol, methanol, isopropanol, cyclohexanone, acetone, butanone or
One of hexamethylene is a variety of, and solid content is 5 ~ 50%.
6. according to claim 2 given up the silicon-carbon cathode material and preparation method thereof of silicon based on photovoltaic, it is characterised in that: institute
When stating step (2) high speed ball milling, the mass ratio of high-purity silicon powder and zirconia ball is 10:(5 ~ 30), the partial size of zirconium oxide is 0.1
~ 3 mm, ball milling speed 100-800rpm.
7. according to claim 2 given up the silicon-carbon cathode material and preparation method thereof of silicon based on photovoltaic, it is characterised in that: institute
Stating the organic carbon source in step (3) is one of phenolic resin, epoxy resin, sucrose, starch, chitosan or glucose or more
Kind.
8. according to claim 2 given up the silicon-carbon cathode material and preparation method thereof of silicon based on photovoltaic, it is characterised in that: institute
Stating the dispersing agent in step (3) is polyvinylpyrrolidone, polyethyleneimine, sodium carboxymethylcellulose or dodecyl benzene sulfonic acid
One of sodium is a variety of.
9. according to claim 2 given up the silicon-carbon cathode material and preparation method thereof of silicon based on photovoltaic, it is characterised in that: institute
Stating solid content when being sanded in step (3) is 5 ~ 50%, and 1000 ~ 3000 rpm of speed is sanded, and 0.5 ~ 10 h of time is sanded.
10. according to claim 2 given up the silicon-carbon cathode material and preparation method thereof of silicon based on photovoltaic, it is characterised in that:
Calcining is that the material after spray drying is warming up to 600 ~ 1000 DEG C of guarantors with the heating rate of 1 ~ 20 DEG C/min in the step (4)
1 ~ 4h of temperature, inert atmosphere are one or more of nitrogen, argon gas or hydrogen.
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