CN106848257A - A kind of preparation method of the carbon coating silicium cathode material of hollow structure - Google Patents
A kind of preparation method of the carbon coating silicium cathode material of hollow structure Download PDFInfo
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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
- H01M4/362—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
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—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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- 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
- H01M4/58—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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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention discloses a kind of preparation method of the carbon coating silicium cathode material of hollow structure, including:Copper powder is cleaned, obtains pre-processing copper powder;By silane coupler, organic solvent according to mass ratio 1:Dissolving forms silanization treatment liquid in 1 addition deionized water;To be sufficiently stirred under condition of water bath heating during pretreatment copper powder adds silanization treatment liquid, stood, dry silanization copper powder;Silanization copper powder, organic carbon source and solvent are well mixed, predecessor is dried to obtain;Tentatively sinter to obtain silicon/carbon/oxidation carbon/carbon-copper composite material;Metal ion therein is removed through Acidwash solution, the silicon/carbon composite of hollow structure is obtained;Double sintering treatment can obtain the carbon coating silicium cathode material of hollow structure.Silicon in negative material prepared by the present invention can be uniformly distributed in the internal layer of carbon coating layer, and hollow structure can effectively suppress the silicon bulk effect in silicon charge and discharge process, effectively improve the cyclical stability of material.
Description
Technical field
The invention belongs to electrochemical energy storage field, and in particular to a kind of preparation of the carbon coating silicium cathode material of hollow structure
Method.
Background technology
As process of industrialization accelerates to be skyrocketed through with economy, energy problem has become the mankind and urgently solves with environmental pollution
Problem certainly, wherein lithium ion battery have become the classic secondary cell of energy field.At present, common lithium ion secondary
Based on graphite-like, this is because graphite-like has good cycle performance and cycle efficieny to the negative material that battery is used.But
Graphite negative electrodes materials theory specific capacity is 372mAh/g, and its lithium storage content is not very good;Simultaneously because the embedding lithium of graphite
Current potential is closer to the deposition potential of lithium, and being charged under larger electric current and low-temperature condition can all make lithium separate out to be formed
Lithium Zhi Jing, therefore there is larger potential safety hazard.Current researcher is actively finding the more excellent negative material of performance, such as silicon
Base, tinbase, lead base etc. can form the metal of electrochemically alloying with lithium, and the Reversible lithium insertion capacity of such alloy anode is much larger than
The theoretical embedding lithium capacity of graphite cathode, wherein silicon based anode material is up to 4200mAh/g and (forms Li22Si5).However, silicon is in hair
Volumetric expansion can reach more than 3 times after raw lithium insertion, the destruction of material structure machinery efflorescence be caused, so as to cycle performance can be caused
Decay is quickly.Be the cyclical stability for improving silicium cathode material, researcher employs the composite of various silicon, it is such as various with
The alloy material and carbon of silicon carry out Si-C composite material of compound preparation etc., although these methods can be to the circulation of silicium cathode
Performance plays certain improvement result, but its mechanism is all to carry out simple physics to silicon to be combined or high temperature carbon coating, not
Inhibitory action fundamentally can played to the Volume Changes in silicium cathode charge and discharge process, be only capable of improving following for silicium cathode short-term
Ring stability.
Therefore it is to push silicium cathode to commercialization to develop a kind of process that can effectively suppress silicium cathode bulk effect
Maximum bottleneck.Control to be proved to be effectively approach, such as patent document CN by carrying out pattern to silicon/carbon composite
105633363A, for template is prepared for hollow porous Si-C composite material, can be carried to a certain extent by cuprous oxide
Its cycle performance high, but silicon is more difficult forms uniform silicon clad on cuprous oxide surface, and the composite of formation is sub- in oxidation
There is certain structural stress in copper mold plate, there is certain destruction to cycle performance after disappearing.
The content of the invention
In view of the shortcomings of the prior art, the present invention provides a kind of preparation side of the carbon coating silicium cathode material of hollow structure
Method, the carbon coating silicium cathode material prepared by this method can effectively suppress the bulk effect in silicon materials cyclic process, and then
Improve the cyclical stability of silicium cathode material.
Technical scheme is as follows:
A kind of preparation method of the carbon coating silicium cathode material of hollow structure, it is comprised the following steps:
(1)Copper powder is cleaned, obtains pre-processing copper powder;
(2)By silane coupler, organic solvent according to mass ratio 1:Dissolving forms silanization treatment liquid in 1 addition deionized water;
(3)To pre-process in copper powder addition silanization treatment liquid, be sufficiently stirred under condition of water bath heating, copper will be filtered after standing
Powder, spontaneously dries to obtain silanization copper powder in air;
(4)Silanization copper powder, organic carbon source and solvent are well mixed, predecessor is then dried to obtain;Predecessor is placed in guarantor
Tentatively sintered in shield property atmosphere, obtained silicon/carbon/oxidation carbon/carbon-copper composite material;
(5)Silicon/carbon/oxidation carbon/carbon-copper composite material is added in Acidwash solution, lasting stirring, treats that cupric oxide reaction therein is complete
After be washed with deionized water, to remove metal ion therein, obtain the silicon/carbon composite of hollow structure;
(6)Silicon/the carbon composite of hollow structure is placed in double sintering treatment in protective atmosphere and can obtain hollow structure
Carbon coating silicium cathode material.
Further scheme, the step(1)In copper powder be selected from particle diameter for 0.2 ~ 1 μm of ultra micro copper powder;The copper powder
Cleaning is to carry out decompression suction filtration to copper powder using absolute ethyl alcohol, acetone, deionized water successively to clean, to remove the residual of Copper Powder Surface
Stay material and activate its surface;The absolute ethyl alcohol, acetone, the quality of deionized water are 50 ~ 100 times of copper powder quality.
Further scheme, the step(2)In silane coupler, the quality of organic solvent be deionized water quality
5~20%;
The silane coupler be selected from alkyls silane coupler, vinyl-based silane, chloropropyl one type of silane, amido one type of silane,
Dredge one or more in base class silane, epoxy radicals one type of silane, acyl-oxygen one type of silane, uride one type of silane, sulfur-bearing one type of silane;
The organic solvent be selected from ethanol, acetone, ethylene glycol, n-hexane in one or two.
Further scheme, the step(3)In condition of water bath heating be:60 ~ 100 DEG C of bath temperature, water bath time 2 ~
10h;The pretreatment copper powder is 5 ~ 15% of silane coupler molar content in silanization treatment liquid.
Further scheme, the step(4)In organic carbon source be selected from glucose, maltose, sucrose, starch, pitch in
One or more, its quality for silanization copper powder quality 20 ~ 60%.
Further scheme, the step(4)In solvent be any one in deionized water, ethanol, methyl alcohol;Make silanization
Solid content is 30 ~ 60wt% in the mixture of copper powder, organic carbon source and solvent.
Further scheme, the step(4)In first sintering condition be:Temperature be 800 ~ 1200 DEG C, the time be 0.5 ~
8h。
Further scheme, the step(4)In presoma drying mode be air drying, vacuum drying, freeze-drying
Or spray drying.
Further scheme, the step(5)In Acidwash solution for pH value for 0.1 ~ 2 aqueous solution of nitric acid.
Further scheme, the step(6)In double sintering condition be:Temperature be 300 ~ 500 DEG C, the time be 10 ~
60min。
The present invention acts on micro- Copper Powder Surface and forms uniform silanization film layer as silicon source by the use of copper surface through silanization,
Then using organic carbon source cladding and noble gas sinter to be formed carbon coating layer by silicon be wrapped in the inside, while copper powder can form oxidation
Copper;Hollow structural carbon coated Si negative material is formed by finally cupric oxide is eroded.The carbon bag obtained by this method
The bulk effect that negative material can effectively suppress in silicon materials cyclic process is covered, and then improves the stable circulation of silicium cathode material
Property.
So beneficial effects of the present invention:
(1)The present invention forms uniform silane film layer using silanization treatment on the surface of micro- copper powder, may be such that silicon is uniformly distributed
On copper powder surface;Simultaneously by the thickness for adjusting the parameter of silanization to control silane film layer, with copper surface silane
Thicknesses of layers controls the content of silicon in carbon coating silicium cathode material.
(2)By silanization treatment Copper Powder Surface coat organic carbon source, control sintering process parameter by silane film layer also
Originally it was silicon, silicon was wrapped in inside carbon-coating after sintering, while copper powder is eroded to form hollow structure, hollow structure can has
Effect suppresses the bulk effect in silicium cathode material charging process, improves the cyclical stability of material.
Brief description of the drawings
Fig. 1 is preparation flow schematic diagram of the invention.
Fig. 2 is the hollow structure carbon coating silicium cathode material thermogravimetric analysis data of preparation in embodiment 3.
Fig. 3 is the hollow structure carbon coating silicium cathode material half-cell 0.1C charging and discharging curves of preparation in embodiment 3.
Fig. 4 is the hollow structure carbon coating silicium cathode material half-cell 0.5C cyclic curves of preparation in embodiment 3.
Specific embodiment
Embodiment 1
As shown in figure 1, a kind of carbon coating silicium cathode material preparation method of hollow structure, it is comprised the following steps:
(1)Micro- copper powder that particle diameter is 0.2 μm is subtracted using the absolute ethyl alcohol of 50 times of its quality, acetone, deionized water successively
Pressure suction filtration cleaning, to wash the residuals of Copper Powder Surface, and activates its surface, obtains pre-processing copper powder;
(2)Alkyls silane coupler 5g, organic solvent ethanol 5g are added in 100g deionized waters and are dissolved, be configured to silane
Change treatment fluid;
(3)By step(1)Pretreatment copper powder add step(2)Silanization treatment liquid in, wherein pretreatment copper powder amount be
The 5% of silane coupler molal weight in silanization treatment liquid, then carries out heating water bath 10h under 600 DEG C of environment, fully stirs
After mixing standing, copper powder is filtered out, be positioned over natural drying in air, obtain silanization treatment copper powder;
(4)By step(3)Silanization treatment copper powder, organic carbon source, solvent be well mixed, wherein organic carbon source be selected from sucrose,
Its mass content is the 20% of silanization treatment copper powder, and subsequent air drying obtains predecessor;By predecessor as protective atmosphere
Lower 800 DEG C of sintering 8h, obtains silicon/carbon/oxidation carbon/carbon-copper composite material;
(5)By step(4)Silicon/carbon/oxidation the carbon/carbon-copper composite material for obtaining is added to pickling in the aqueous solution of nitric acid that pH value is 0.1,
Lasting stirring, is washed with deionized water after copper reaction completely to be oxidized, removes metal ion therein, obtain the silicon of hollow structure/
Carbon composite;
(6)Silicon/the carbon composite of hollow structure is placed in protective atmosphere by 300 DEG C of sintering 60min double sinterings
Reason can obtain the carbon coating silicium cathode material of hollow structure.
Embodiment 2
(1)Micro- copper powder that particle diameter is 0.4 μm is subtracted using the absolute ethyl alcohol of 60 times of its quality, acetone, deionized water successively
Pressure suction filtration cleaning, washes the residuals of Copper Powder Surface, and activates its surface, obtains pre-processing copper powder;
(2)Vinyl-based silane coupler 10g, organic solvent propyl alcohol 10g are added in deionized water 100g and are dissolved, its configuration
Into silanization treatment liquid;
(3)By step(1)Pretreatment copper powder adds step(2)Silanization treatment liquid in, wherein pretreatment copper powder be silanization
The 5% of silane coupler molal weight in treatment fluid, then carries out heating water bath 8h under 700 DEG C of environment, is sufficiently stirred for standing
Afterwards, copper powder is filtered out, natural drying in air is positioned over, silanization treatment copper powder is obtained;
(4)By step(3)Silanization treatment copper powder, organic carbon source, solvent be well mixed, wherein organic carbon source be selected from grape
Sugar, its mass content is the 30% of silanization treatment copper powder, and then vacuum drying obtains predecessor;By predecessor as protectiveness
The lower 800 DEG C of sintering 8h of atmosphere, obtains silicon/carbon/oxidation carbon/carbon-copper composite material;
(5)By step(4)Silicon/carbon/oxidation the carbon/carbon-copper composite material for obtaining is added to pickling in the aqueous solution of nitric acid that pH is 0.5, holds
Continuous stirring, is washed with deionized water after copper reaction completely to be oxidized, removes metal ion therein, obtains the silicon/carbon of hollow structure
Composite;
(6)Silicon/the carbon composite of hollow structure is placed in protective atmosphere by 350 DEG C of sintering 50min double sinterings
Reason can obtain the carbon coating silicium cathode material of hollow structure.
Embodiment 3
(1)Micro- copper powder that particle diameter is 0.6 μm is subtracted using the absolute ethyl alcohol of 70 times of its quality, acetone, deionized water successively
Pressure suction filtration cleaning, washes the residuals of Copper Powder Surface, activates its surface, obtains pre-processing copper powder;
(2)Chloropropyl one type of silane coupling agent 15g, organic solvent ethanol 15g are added in deionized water 100g and are dissolved, be configured to
Silanization treatment liquid;
(3)By step(1)Pretreatment copper powder adds step(2)Silanization treatment liquid in, wherein pretreatment copper powder be silanization
The 7% of silane coupler molal weight in treatment fluid, then carries out heating water bath 6h under 800 DEG C of environment, is sufficiently stirred for standing
Afterwards, copper powder is filtered out, natural drying in air is positioned over, silanization treatment copper powder is obtained;
(4)By step(3)Silanization treatment copper powder, organic carbon source, solvent be well mixed, wherein organic carbon source be selected from starch,
Its mass content is the 40% of silanization treatment copper powder, and subsequent freeze-drying obtains predecessor;By predecessor as protective atmosphere
Lower 800 DEG C of sintering 8h, obtains silicon/carbon/oxidation carbon/carbon-copper composite material;
(5)By step(4)Silicon/carbon/oxidation the carbon/carbon-copper composite material for obtaining is added to pickling in the aqueous solution of nitric acid that pH is 1.0, holds
Continuous stirring, is washed with deionized water after copper reaction completely to be oxidized, removes metal ion therein, obtains the silicon/carbon of hollow structure
Composite;
(6)Silicon/the carbon composite of hollow structure is placed in protective atmosphere by 400 DEG C of sintering 40min double sinterings
Reason can obtain the carbon coating silicium cathode material of hollow structure.
It is the chemical property of hollow structure carbon coating silicium cathode material prepared by the detection present invention, using 2016 buttons
Battery carries out electrochemistry evaluation and test to it.The hollow structure carbon coating silicium cathode material prepared using embodiment 3 as positive pole, with
Positive active material:Conductive agent Super P:Bonding agent Kynoar (PVDF)=80:10:10 mass ratio carries out conjunction slurry,
It is subsequently coated at 120 DEG C of utter misery aluminum foil current collector surface baking 2h and obtains anode pole piece, full of assembling in Ar glove boxes
Into button cell, wherein metal lithium sheet is that, to electrode, clegard2400 is barrier film, the LiPF6/EC+ DMC+FEC of 1mol/L
(70:20:10) solution is electrolyte, and constant current charge-discharge test is carried out using Land battery test systems.
The hollow structure carbon coating silicium cathode material thermal gravimetric analysis curve that the present embodiment 3 is prepared is illustrated in figure 2, is tied
Silicon mass content is 10.21% in the hollow structure carbon coating silicium cathode material that fruit display embodiment 3 is prepared;
The hollow structure carbon coating silicium cathode material prepared in embodiment 3 is illustrated in figure 3 to lithium half-cell 0.2C multiplying powers
First charge-discharge curve;Fig. 4 be in embodiment 3 the hollow structure carbon coating silicium cathode material for preparing to 1C times of lithium half-cell
Rate cyclic curve.Synthesis result analysis finds, the hollow structure carbon coating silicium cathode material prepared using the present invention program
0.1C initial charges specific capacity is 734mAh/g;The specific discharge capacity after 25 weeks is circulated under 0.5C multiplying powers still to keep
527mAh/g, capability retention is the 81.8% of initial discharge specific capacity (644mAh/g).Result above shows by this technology side
Hollow structure carbon coating silicium cathode material prepared by case embodies good specific discharge capacity and cyclical stability.
Embodiment 4
(1)Micro- copper powder that particle diameter is 0.8 μm is subtracted using the absolute ethyl alcohol of 80 times of its quality, acetone, deionized water successively
Pressure suction filtration cleaning, washes the residuals of Copper Powder Surface, activates its surface, obtains pre-processing copper powder;
(2)Amido one type of silane coupling agent 10g, organic solvent ethylene glycol 10g are added in deionized water 100g and are dissolved, be configured to
Silanization treatment liquid;
(3)By step(1)Pretreatment copper powder adds step(2)Silicon in physics and chemistry liquid, wherein pretreatment copper powder is silane treatment
The 9% of silane coupler molal weight in liquid, then carries out heating water bath 4h under 900 DEG C of environment, after being sufficiently stirred for standing, mistake
Copper powder is leached, natural drying in air is positioned over, silanization treatment copper powder is obtained;
(4)By step(3)Silanization treatment copper powder, organic carbon source, solvent be well mixed, wherein organic carbon source be selected from malt
Sugar, its mass content is the 50% of silanization treatment copper powder, and subsequent spray is dried to obtain predecessor;By predecessor as protectiveness
The lower 800 DEG C of sintering 8h of atmosphere, obtains silicon/carbon/oxidation carbon/carbon-copper composite material;
(5)By step(4)Silicon/carbon/oxidation the carbon/carbon-copper composite material for obtaining is added to pickling in the aqueous solution of nitric acid that pH is 1.5, holds
Continuous stirring, is washed with deionized water after copper reaction completely to be oxidized, removes metal ion therein, obtains the silicon/carbon of hollow structure
Composite;
(6)Silicon/the carbon composite of hollow structure is placed in protective atmosphere by 450 DEG C of sintering 30min double sinterings
Reason can obtain the carbon coating silicium cathode material of hollow structure.
Embodiment 5
(1)Micro- copper powder that particle diameter is 1 μm is depressurized using the absolute ethyl alcohol of 90 times of its quality, acetone, deionized water successively
Suction filtration is cleaned, and washes the residuals of Copper Powder Surface, activates its surface, obtains pre-processing copper powder;
(2)Ureide derivative silane coupler 20g, organic solvent-acetone 20g are added in deionized water 100g and are dissolved, be configured to silicon
Alkanisation treatment fluid;
(3)By step(1)Pretreatment copper powder adds step(2)Silicon in physics and chemistry liquid, wherein pretreatment copper powder is silane treatment
The 15% of silane coupler molal weight in liquid, then carries out heating water bath 2h under 1000 DEG C of environment, after being sufficiently stirred for standing,
Copper powder is filtered out, natural drying in air is positioned over, silanization treatment copper powder is obtained;
(4)By step(3)Silanization treatment copper powder, organic carbon source, solvent be well mixed, wherein organic carbon source be selected from sucrose,
Its mass content is the 20% of silanization treatment copper powder, and subsequent freeze-drying obtains predecessor;By predecessor as protective atmosphere
Lower 800 DEG C of sintering 8h, obtains silicon/carbon/oxidation carbon/carbon-copper composite material;
(5)By step(4)Silicon/carbon/oxidation the carbon/carbon-copper composite material for obtaining is added to pickling in the aqueous solution of nitric acid that pH is 2.0, holds
Continuous stirring, is washed with deionized water after copper reaction completely to be oxidized, removes metal ion therein, obtains the silicon/carbon of hollow structure
Composite;
(6)Silicon/the carbon composite of hollow structure is placed in protective atmosphere by 600 DEG C of sintering 10min double sinterings
Reason can obtain the carbon coating silicium cathode material of hollow structure.
Embodiment 6
(1)Micro- copper powder that particle diameter is 1 μm is depressurized using the absolute ethyl alcohol of 100 times of its quality, acetone, deionized water successively
Suction filtration is cleaned, and washes the residuals of Copper Powder Surface, activates its surface, obtains pre-processing copper powder;
(2)Epoxy radicals one type of silane, acyl-oxygen one type of silane and sulfur-bearing one type of silane coupling agent 15g, organic solvent-normal hexane 15g are added to
Dissolved in deionized water 100g, be configured to silanization treatment liquid;
(3)By step(1)Pretreatment copper powder adds step(2)Silicon in physics and chemistry liquid, wherein pretreatment copper powder is silane treatment
The 12% of silane coupler molal weight in liquid, then carries out heating water bath 10h under 600 DEG C of environment, after being sufficiently stirred for standing,
Copper powder is filtered out, natural drying in air is positioned over, silanization treatment copper powder is obtained;
(4)By step(3)Silanization treatment copper powder, organic carbon source, solvent be well mixed, wherein organic carbon source be selected from pitch,
Its mass content is the 40% of silanization treatment copper powder, and then vacuum drying obtains predecessor;By predecessor as protective atmosphere
Lower 800 DEG C of sintering 8h, obtains silicon/carbon/oxidation carbon/carbon-copper composite material;
(5)By step(4)Silicon/carbon/oxidation the carbon/carbon-copper composite material for obtaining is added to pickling in the aqueous solution of nitric acid that pH is 1.5, holds
Continuous stirring, is washed with deionized water after copper reaction completely to be oxidized, removes metal ion therein, obtains the silicon/carbon of hollow structure
Composite;
(6)Silicon/the carbon composite of hollow structure is placed in protective atmosphere by 450 DEG C of sintering 30min double sinterings
Reason can obtain the carbon coating silicium cathode material of hollow structure.
Above content is only to structure example of the present invention and explanation, affiliated those skilled in the art couple
Described specific embodiment is made various modifications or supplement or is substituted using similar mode, without departing from invention
Structure surmounts scope defined in the claims, all should belong to protection scope of the present invention.
Claims (10)
1. the preparation method of the carbon coating silicium cathode material of a kind of hollow structure, it is characterised in that comprise the following steps:
(1)Copper powder is cleaned, obtains pre-processing copper powder;
(2)By silane coupler, organic solvent according to mass ratio 1:Dissolving forms silanization treatment liquid in 1 addition deionized water;
(3)To pre-process in copper powder addition silanization treatment liquid, be sufficiently stirred under condition of water bath heating, copper will be filtered after standing
Powder, spontaneously dries to obtain silanization copper powder in air;
(4)Silanization copper powder, organic carbon source and solvent are well mixed, predecessor is then dried to obtain;Predecessor is placed in guarantor
Tentatively sintered in shield property atmosphere, obtained silicon/carbon/oxidation carbon/carbon-copper composite material;
(5)Silicon/carbon/oxidation carbon/carbon-copper composite material is added in Acidwash solution, lasting stirring, treats that cupric oxide reaction therein is complete
After be washed with deionized water, to remove metal ion therein, obtain the silicon/carbon composite of hollow structure;
(6)Silicon/the carbon composite of hollow structure is placed in double sintering treatment in protective atmosphere and can obtain hollow structure
Carbon coating silicium cathode material.
2. preparation method according to claim 1, it is characterised in that:The step(1)In copper powder be selected from particle diameter be 0.2
~ 1 μm of ultra micro copper powder;The cleaning of the copper powder is to carry out decompression to copper powder using absolute ethyl alcohol, acetone, deionized water successively to take out
Filtering is washed, to remove the residuals of Copper Powder Surface and activate its surface;The absolute ethyl alcohol, acetone, the quality of deionized water
It is 50 ~ 100 times of copper powder quality.
3. preparation method according to claim 1, it is characterised in that:The step(2)In silane coupler, You Jirong
The quality of agent is the 5 ~ 20% of deionized water quality;
The silane coupler be selected from alkyls silane coupler, vinyl-based silane, chloropropyl one type of silane, amido one type of silane,
Dredge one or more in base class silane, epoxy radicals one type of silane, acyl-oxygen one type of silane, uride one type of silane, sulfur-bearing one type of silane;
The organic solvent be selected from ethanol, acetone, ethylene glycol, n-hexane in one or two.
4. preparation method according to claim 1, it is characterised in that:The step(3)In condition of water bath heating be:Water
60 ~ 100 DEG C of bath temperature, 2 ~ 10h of water bath time;The pretreatment copper powder is silane coupler molar content in silanization treatment liquid
5 ~ 15%.
5. preparation method according to claim 1, it is characterised in that:The step(4)In organic carbon source be selected from grape
One or more in sugar, maltose, sucrose, starch, pitch, its quality is the 20 ~ 60% of silanization copper powder quality.
6. preparation method according to claim 1, it is characterised in that:The step(4)In solvent be deionized water, second
Any one in alcohol, methyl alcohol;Solid content is 30 ~ 60wt% in making the mixture of silanization copper powder, organic carbon source and solvent.
7. preparation method according to claim 1, it is characterised in that:The step(4)In first sintering condition be:Temperature
Spend for 800 ~ 1200 DEG C, time are 0.5 ~ 8h.
8. preparation method according to claim 1, it is characterised in that:The step(4)In presoma drying mode be
Air drying, vacuum drying, freeze-drying or spray drying.
9. preparation method according to claim 1, it is characterised in that:The step(5)In Acidwash solution be for pH value
0.1 ~ 2 aqueous solution of nitric acid.
10. preparation method according to claim 1, it is characterised in that:The step(6)In double sintering condition be:
Temperature is 300 ~ 500 DEG C, the time is 10 ~ 60min.
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