CN108899488A - Modified carbon-coated silicon monoxide composite material, preparation method and application thereof - Google Patents
Modified carbon-coated silicon monoxide composite material, preparation method and application thereof Download PDFInfo
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- CN108899488A CN108899488A CN201810620047.6A CN201810620047A CN108899488A CN 108899488 A CN108899488 A CN 108899488A CN 201810620047 A CN201810620047 A CN 201810620047A CN 108899488 A CN108899488 A CN 108899488A
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- 239000002131 composite material Substances 0.000 title claims abstract description 67
- 150000001721 carbon Chemical class 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 title abstract 8
- 239000000463 material Substances 0.000 claims abstract description 78
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 59
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 48
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000005011 phenolic resin Substances 0.000 claims abstract description 43
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 43
- 238000010438 heat treatment Methods 0.000 claims abstract description 41
- 238000003756 stirring Methods 0.000 claims abstract description 35
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 22
- 238000001291 vacuum drying Methods 0.000 claims abstract description 14
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 71
- 239000010703 silicon Substances 0.000 claims description 71
- 238000000576 coating method Methods 0.000 claims description 65
- 239000011248 coating agent Substances 0.000 claims description 64
- 229910052799 carbon Inorganic materials 0.000 claims description 35
- 235000019441 ethanol Nutrition 0.000 claims description 23
- 238000003763 carbonization Methods 0.000 claims description 20
- 239000011863 silicon-based powder Substances 0.000 claims description 19
- 239000011261 inert gas Substances 0.000 claims description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 230000004048 modification Effects 0.000 claims description 14
- 238000012986 modification Methods 0.000 claims description 14
- 230000003647 oxidation Effects 0.000 claims description 13
- 238000007254 oxidation reaction Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000005516 engineering process Methods 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000000843 powder Substances 0.000 abstract description 2
- 238000010000 carbonizing Methods 0.000 abstract 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 238000007599 discharging Methods 0.000 description 6
- 238000009210 therapy by ultrasound Methods 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 239000011149 active material Substances 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- -1 graphite Alkene Chemical class 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
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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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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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
- H01M4/62—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
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
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Abstract
The invention discloses a modified carbon-coated silicon monoxide composite material, a preparation method and application thereof, wherein the preparation method comprises the following steps: dissolving phenolic resin in ethanol to obtain a material A; adding graphene oxide into the material A, uniformly mixing, adding silicon monoxide powder, heating and stirring until the mixture is evaporated to dryness, and then carrying out vacuum drying to obtain a material B; and carbonizing the material B to obtain the modified carbon-coated silicon monoxide composite material. The preparation method is simple and easy to operate, has low cost, is suitable for large-scale production, and the obtained composite material has a three-dimensional layered three-dimensional structure, can relieve huge stress change, is used in a lithium ion battery, and has high theoretical capacity and first coulombic efficiency.
Description
Technical field
The present invention relates to nano silica-base material technical fields more particularly to a kind of modified carbon coating to aoxidize sub- silicon composite wood
Material, preparation method and applications.
Background technique
Graphite is cheap as one kind, and good conductivity and stable material are wide in negative electrode of lithium ion battery field in recent years
It applies generally.However, graphite cathode material is widely believed that capacity is relatively low (theoretical capacity 372mAh/g), needed for not being able to satisfy compared with
The requirement of high energy density.In contrast, from the point of view of the silicon-carbon cathode material performance of current commercialization, maximum advantage exists
In the promotion of specific capacity, silicon-carbon cathode can be obviously improved battery energy density, to make electricity in the constant situation of volume or weight
Pond is packed into more electricity.However aoxidize sub- silicon there are biggish bulk effect (>100%), make it can powder in charge and discharge process
Change and peeled off from collector, so that losing electrical contact between active material and active material, active material and collector, simultaneously
New solid-phase electrolyte layer SEI is constantly formed, the deterioration of chemical property is eventually led to.
The silicon-carbon cathode material of existing market mostly uses core-shell structure, it is intended to promote silicon/oxidation Asia silicon face and lead
Then electric energy power is then directly applied in battery material by mixing with graphite.However, silicon/silicon oxygen particle surface carbon-coating
It is rigid structure, without the effect for alleviating volume change, and apparent rupture can occurs with the process of charge and discharge.
Summary of the invention
Technical problems based on background technology, the invention proposes a kind of modified carbon coatings to aoxidize sub- silicon composite wood
Material, preparation method and applications, the preparation method is simple to operation, and cost is relatively low, and suitable for mass production, what is obtained is compound
Material has three-layer laminated stereochemical structure, can alleviate huge stress variation, is used in lithium ion battery, theoretical capacity and for the first time
Coulombic efficiency is high.
A kind of modified carbon coating proposed by the present invention aoxidizes the preparation method of sub- silicon composite, includes the following steps:
S1, it phenolic resin is dissolved in ethyl alcohol obtains material A;
S2, addition graphene oxide is uniformly mixed in material A, is added and is aoxidized sub- Si powder, heating stirring is to being evaporated, so
After be dried in vacuo to obtain material B;
S3, material B progress carbonization treatment is obtained into the modified sub- silicon composite of carbon coating oxidation.
Preferably, in S1, the mass volume ratio of phenolic resin and ethyl alcohol is 0.1-1:20-80g/mL.
Preferably, the concrete operations of S1 are:Phenolic resin is added in ethyl alcohol, ultrasonic disperse after stirring makes phenolic resin
Dissolution obtains material A.
Preferably, the time of ultrasonic disperse is 0.2-1h.
Preferably, in S2, the mass ratio of the phenolic resin in graphene oxide and material A is 1-1.5:2-5.
Preferably, in S2, the size for aoxidizing sub- Si powder is 1-10 μm.
Preferably, in S2, for heating stirring to during being evaporated, temperature is 60-120 DEG C;Vacuum drying temperature is
80-150 DEG C, the vacuum drying time is 12-24h.
Preferably, in S3, the concrete technology of the carbonization treatment is:In the atmosphere of inert gas, with 2-10 DEG C/
The heating rate of min is warming up to 600-1000 DEG C, constant temperature 2-6h.
Preferably, the inert gas is one of nitrogen, argon gas or two kinds of mixture.
Preferably, heating rate is 2 DEG C/min.
Preferably, it is aoxidized in sub- silicon composite in obtained modification carbon coating, the mass content of carbon is 1-10wt%.
A kind of modified carbon coating that the present invention also proposes aoxidizes sub- silicon composite, is aoxidized using the modified carbon coating sub-
The preparation method of silicon composite is prepared.
One kind that the present invention also proposes modified carbon coating aoxidizes sub- silicon composite as negative electrode of lithium ion battery material
The application of material.
During carbonization treatment, heating rate influences the effect that presoma is reduced will lead if heating rate is too fast
Cause precursor mixture uneven heating, be not achieved ideal effect, in the present invention, specifically control heating rate be 2-10 DEG C/
Min is heated evenly precursor mixture (material B), and simultaneous reactions are abundant, realizes optimal effect.
Preferably, in S2, heating stirring is to during being evaporated, further including ultrasonic treatment.
The present invention realizes uniform carbon coating in silicon/silicon oxygen particle surface by way of being pyrolyzed phenolic resin, and graphite
Alkene has apparent two-dimensional structure and size is larger, mutual intercalation, easily forms the special carbon net of elastic construction.This " graphite
Alkene-silicon-carbon-graphene " sandwich can allow for active material to change during removal lithium embedded with the variation of material volume
And do not rupture, therefore there is constraint and buffer because of the volume and dusting due to stress variation the phenomenon that, and have prevent electrolyte to
Activated centre infiltration, keeps the effect at stable interface and SEI.Preparation method of the invention is simple to operation, and cost is relatively low, energy
Applied to a variety of silica-base materials, adaptability is good, and suitable for mass production.
Detailed description of the invention
Fig. 1 is the structural schematic diagram that modified carbon coating proposed by the present invention aoxidizes sub- silicon composite;
Fig. 2 is the XRD curve that modification carbon coating prepared by the embodiment of the present invention 1 aoxidizes sub- silicon composite;
Fig. 3 is the charging and discharging curve figure that modification carbon coating prepared by the embodiment of the present invention 1 aoxidizes sub- silicon composite;
Fig. 4 is the XRD curve that modification carbon coating prepared by the embodiment of the present invention 2 aoxidizes sub- silicon composite;
Fig. 5 is the charging and discharging curve figure that modification carbon coating prepared by the embodiment of the present invention 2 aoxidizes sub- silicon composite;
Fig. 6 is the XRD curve that modification carbon coating prepared by the embodiment of the present invention 3 aoxidizes sub- silicon composite;
Fig. 7 is the charging and discharging curve figure that modification carbon coating prepared by the embodiment of the present invention 3 aoxidizes sub- silicon composite.
Specific embodiment
In the following, technical solution of the present invention is described in detail by specific embodiment.
Embodiment 1
A kind of modified carbon coating proposed by the present invention aoxidizes the preparation method of sub- silicon composite, includes the following steps:
S1,0.2g phenolic resin is added in 20ml ethyl alcohol, ultrasonic disperse 0.5h after stirring makes phenolic resin dissolve to obtain
Material A;
S2, addition graphene oxide is uniformly mixed in material A, wherein the phenolic resin in graphene oxide and material A
Mass ratio be 1:2, it is added and aoxidizes sub- Si powder, be transferred on magnetic stirring apparatus, then heating stirring carries out vacuum to being evaporated
It is dried to obtain material B;Wherein, the size for aoxidizing sub- Si powder is 2 μm;In heating stirring to during being evaporated, temperature
It is 60 DEG C;Vacuum drying temperature is 80 DEG C, and the vacuum drying time is for 24 hours;In heating stirring to during being evaporated, also wrap
Include ultrasonic treatment;
S3, material B progress carbonization treatment is obtained into the modified sub- silicon composite of carbon coating oxidation;Its yield is
74%;Wherein, the concrete technology of the carbonization treatment is:In the atmosphere of nitrogen, it is warming up to the heating rate of 2 DEG C/min
700 DEG C, constant temperature 2h.
Embodiment 2
A kind of modified carbon coating proposed by the present invention aoxidizes the preparation method of sub- silicon composite, includes the following steps:
S1, phenolic resin is added in ethyl alcohol, ultrasonic disperse after stirring makes phenolic resin dissolve to obtain material A;
S2, addition graphene oxide is uniformly mixed in material A, is added and is aoxidized sub- Si powder, is transferred to magnetic stirring apparatus
On, then heating stirring is dried in vacuo to obtain material B to being evaporated;
S3, material B progress carbonization treatment is obtained into the modified sub- silicon composite of carbon coating oxidation;Yield is 81%;
Wherein, in S1, the quality of phenolic resin is 0.4g, and the volume of ethyl alcohol is 40mL;The time of ultrasonic disperse is
0.5h;
In S2, the mass ratio of the phenolic resin in graphene oxide and material A is 1:3;The sub- Si powder of oxidation
Having a size of 4 μm;In heating stirring to during being evaporated, temperature is 80 DEG C;Vacuum drying temperature is 100 DEG C, vacuum drying
Time be for 24 hours;Heating stirring to during being evaporated, further include ultrasonic treatment;
In S3, the concrete technology of the carbonization treatment is:In the atmosphere of inert gas, with the heating speed of 10 DEG C/min
Rate is warming up to 800 DEG C, constant temperature 4h;The inert gas is argon gas.
Embodiment 3
A kind of modified carbon coating proposed by the present invention aoxidizes the preparation method of sub- silicon composite, includes the following steps:
S1, phenolic resin is added in ethyl alcohol, ultrasonic disperse after stirring makes phenolic resin dissolve to obtain material A;
S2, addition graphene oxide is uniformly mixed in material A, is added and is aoxidized sub- Si powder, is transferred to magnetic stirring apparatus
On, then heating stirring is dried in vacuo to obtain material B to being evaporated;
S3, material B progress carbonization treatment is obtained into the modified sub- silicon composite of carbon coating oxidation;Yield is 90%;
Wherein, in S1, the quality of phenolic resin is 0.6g, and the volume of ethyl alcohol is 60mL;The time of ultrasonic disperse is
0.5h;
In S2, the mass ratio of the phenolic resin in graphene oxide and material A is 1:4;
In S2, the size for aoxidizing sub- Si powder is 4 μm;
In S2, in heating stirring to during being evaporated, temperature is 80 DEG C;Vacuum drying temperature is 100 DEG C, vacuum
The dry time is for 24 hours;
In S3, the concrete technology of the carbonization treatment is:In the atmosphere of inert gas, with the heating speed of 5 DEG C/min
Rate is warming up to 900 DEG C, constant temperature 6h;The inert gas is argon gas.
Embodiment 4
A kind of modified carbon coating proposed by the present invention aoxidizes the preparation method of sub- silicon composite, includes the following steps:
S1, phenolic resin is added in ethyl alcohol, ultrasonic disperse after stirring makes phenolic resin dissolve to obtain material A;
S2, addition graphene oxide is uniformly mixed in material A, is added and is aoxidized sub- Si powder, is transferred to magnetic stirring apparatus
On, then heating stirring is dried in vacuo to obtain material B to being evaporated;
S3, material B progress carbonization treatment is obtained into the modified sub- silicon composite of carbon coating oxidation;Yield is 90%;
Wherein, in S1, the quality of phenolic resin is 0.8g, and the volume of ethyl alcohol is 80mL;The time of ultrasonic disperse is
0.5h;
In S2, the mass ratio of the phenolic resin in graphene oxide and material A is 1:5;
In S2, the size for aoxidizing sub- Si powder is 8 μm;
In S2, in heating stirring to during being evaporated, temperature is 80 DEG C;Vacuum drying temperature is 100 DEG C, vacuum
The dry time is for 24 hours;
In S3, the concrete technology of the carbonization treatment is:In the atmosphere of inert gas, with the heating speed of 2 DEG C/min
Rate is warming up to 1000 DEG C, constant temperature 6h;The inert gas is argon gas.
Embodiment 5
A kind of modified carbon coating proposed by the present invention aoxidizes the preparation method of sub- silicon composite, includes the following steps:
S1, it phenolic resin is dissolved in ethyl alcohol obtains material A;
S2, addition graphene oxide is uniformly mixed in material A, is added and is aoxidized sub- Si powder, heating stirring is to being evaporated, so
After be dried in vacuo to obtain material B;
S3, material B progress carbonization treatment is obtained into the modified sub- silicon composite of carbon coating oxidation.
Embodiment 6
A kind of modified carbon coating proposed by the present invention aoxidizes the preparation method of sub- silicon composite, includes the following steps:
S1, it phenolic resin is dissolved in ethyl alcohol obtains material A;
S2, addition graphene oxide is uniformly mixed in material A, is added and is aoxidized sub- Si powder, heating stirring is to being evaporated, so
After be dried in vacuo to obtain material B;
S3, material B progress carbonization treatment is obtained into the modified sub- silicon composite of carbon coating oxidation;
Wherein, in S1, the mass volume ratio of phenolic resin and ethyl alcohol is 1:20g/mL;
The concrete operations of S1 are:Phenolic resin is added in ethyl alcohol, ultrasonic disperse after stirring makes phenolic resin dissolve to obtain
Material A;The time of ultrasonic disperse is 1h;
In S2, the mass ratio of the phenolic resin in graphene oxide and material A is 1:5;
In S2, the size for aoxidizing sub- Si powder is 1 μm;
In S2, in heating stirring to during being evaporated, temperature is 120 DEG C;Vacuum drying temperature is 80 DEG C, vacuum
The dry time is for 24 hours;
In S2, heating stirring is to during being evaporated, further including ultrasonic treatment;
In S3, the concrete technology of the carbonization treatment is:In the atmosphere of inert gas, with the heating speed of 2 DEG C/min
Rate is warming up to 1000 DEG C, constant temperature 2h;The inert gas is argon gas;
It is aoxidized in sub- silicon composite in obtained modification carbon coating, the mass content of carbon is 1wt%.
A kind of modified carbon coating that the present invention also proposes aoxidizes sub- silicon composite, compound using the carbon modified coated Si
The preparation method of material is prepared.
One kind that the present invention also proposes modified carbon coating aoxidizes sub- silicon composite as negative electrode of lithium ion battery material
The application of material.
Embodiment 7
A kind of modified carbon coating proposed by the present invention aoxidizes the preparation method of sub- silicon composite, includes the following steps:
S1, it phenolic resin is dissolved in ethyl alcohol obtains material A;
S2, addition graphene oxide is uniformly mixed in material A, is added and is aoxidized sub- Si powder, heating stirring is to being evaporated, so
After be dried in vacuo to obtain material B;
S3, material B progress carbonization treatment is obtained into the modified sub- silicon composite of carbon coating oxidation;
Wherein, in S1, the mass volume ratio of phenolic resin and ethyl alcohol is 0.1:80g/mL;
The concrete operations of S1 are:Phenolic resin is added in ethyl alcohol, ultrasonic disperse after stirring makes phenolic resin dissolve to obtain
Material A;The time of ultrasonic disperse is 0.2h;
In S2, the mass ratio of the phenolic resin in graphene oxide and material A is 1.5:2;
In S2, the size for aoxidizing sub- Si powder is 10 μm;
In S2, in heating stirring to during being evaporated, temperature is 60 DEG C;Vacuum drying temperature is 150 DEG C, vacuum
The dry time is 12h;
In S2, heating stirring to during being evaporated, further include ultrasonic treatment;
In S3, the concrete technology of the carbonization treatment is:In the atmosphere of inert gas, with the heating speed of 10 DEG C/min
Rate is warming up to 600 DEG C, constant temperature 6h;The inert gas is nitrogen;
It is aoxidized in sub- silicon composite in obtained modification carbon coating, the mass content of carbon is 10wt%.
A kind of modified carbon coating that the present invention also proposes aoxidizes sub- silicon composite, is aoxidized using the modified carbon coating sub-
The preparation method of silicon composite is prepared.
A kind of modified carbon coating that the present invention also proposes aoxidizes sub- silicon composite as lithium ion battery negative material
Using.
Embodiment 8
A kind of modified carbon coating proposed by the present invention aoxidizes the preparation method of sub- silicon composite, includes the following steps:
S1, it phenolic resin is dissolved in ethyl alcohol obtains material A;
S2, addition graphene oxide is uniformly mixed in material A, is added and is aoxidized sub- Si powder, heating stirring is to being evaporated, so
After be dried in vacuo to obtain material B;
S3, material B progress carbonization treatment is obtained into the carbon modified cladding silicon composite with three-layer laminated structure;
Wherein, in S1, the mass volume ratio of phenolic resin and ethyl alcohol is 0.5:60g/mL;
The concrete operations of S1 are:Phenolic resin is added in ethyl alcohol, ultrasonic disperse after stirring makes phenolic resin dissolve to obtain
Material A;The time of ultrasonic disperse is 0.6h;
In S2, the mass ratio of the phenolic resin in graphene oxide and material A is 1.3:3.7;
In S2, the size for aoxidizing sub- Si powder is 6 μm;
In S2, in heating stirring to during being evaporated, temperature is 85 DEG C;Vacuum drying temperature is 120 DEG C, vacuum
The dry time is 15h;
In S2, heating stirring to during being evaporated, further include ultrasonic treatment;
In S3, the concrete technology of the carbonization treatment is:In the atmosphere of inert gas, with the heating speed of 2 DEG C/min
Rate is warming up to 850 DEG C, constant temperature 4h;
The inert gas is the mixture of nitrogen, argon gas;
It is aoxidized in sub- silicon composite in obtained modification carbon coating, the mass content of carbon is 7wt%.
A kind of modified carbon coating that the present invention also proposes aoxidizes sub- silicon composite, compound using the carbon modified coated Si
The preparation method of material is prepared.
One kind that the present invention also proposes modified carbon coating aoxidizes sub- silicon composite as negative electrode of lithium ion battery material
The application of material.
Fig. 1 is the structural schematic diagram that modified carbon coating proposed by the present invention aoxidizes sub- silicon composite;As shown in Figure 1, originally
Inventing the modified carbon coating and aoxidizing sub- silicon composite is special " graphene-silicon-carbon-graphene " sandwich, wherein
The conductive capability of material can be greatlyd improve by aoxidizing the sub- surface coated carbon-coating of silicon particle, and three-layer laminated structure facilitates
The stress variation during removal lithium embedded is buffered, its stability is improved.
(SiOC-700 DEG C) progress performance of sub- silicon composite is aoxidized to the modification carbon coating prepared in the embodiment of the present invention 1
Detection, XRD curve is as shown in Fig. 2, its charging and discharging curve is as shown in Figure 3;As shown in Figure 2, it is obtained under 700 DEG C of sintering temperatures
Modified carbon coating aoxidizes the brilliant as not changing of sub- silicon composite;From the figure 3, it may be seen that its initial charge capacity is
1252.2mAh/g (0.8V), head effect are 55.3%.
(SiOC-800 DEG C) progress performance of sub- silicon composite is aoxidized to the modification carbon coating prepared in the embodiment of the present invention 2
Detection, XRD curve is as shown in figure 4, its charging and discharging curve is as shown in Figure 5;As shown in Figure 4, it is obtained under 800 DEG C of sintering temperatures
Modified carbon coating aoxidizes the brilliant as not changing of sub- silicon composite;As shown in Figure 5, initial charge capacity is
1343mAh/g (0.8V), head effect are 59%.
(SiOC-900 DEG C) progress performance of sub- silicon composite is aoxidized to the modification carbon coating prepared in the embodiment of the present invention 3
Detection, XRD curve is as shown in fig. 6, its charging and discharging curve is as shown in Figure 7;It will be appreciated from fig. 6 that obtained under 900 DEG C of sintering temperatures
The modified sub- silicon composite of carbon coating oxidation has occurred apparent disproportionation phenomenon and generates elemental silicon;As shown in Figure 7, initial charge
Capacity is 1427mAh/g (0.8V), and head effect is 65%.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (10)
1. the preparation method that a kind of modified carbon coating aoxidizes sub- silicon composite, which is characterized in that include the following steps:
S1, it phenolic resin is dissolved in ethyl alcohol obtains material A;
S2, graphene oxide be added in material A be uniformly mixed, be added and aoxidize sub- Si powder, heating stirring to being evaporated, then into
Row vacuum drying obtains material B;
S3, material B progress carbonization treatment is obtained into the modified sub- silicon composite of carbon coating oxidation.
2. being modified the preparation method that carbon coating aoxidizes sub- silicon composite according to claim 1, which is characterized in that in S1
In, the mass volume ratio of phenolic resin and ethyl alcohol is 0.1-1:20-80g/mL.
3. the preparation method that modified carbon coating according to claim 1 or claim 2 aoxidizes sub- silicon composite, which is characterized in that S1
Concrete operations be:Phenolic resin is added in ethyl alcohol, ultrasonic disperse after stirring makes phenolic resin dissolve to obtain material A;It is preferred that
Ground, the time of ultrasonic disperse are 0.2-1h.
4. modified carbon coating described in any one of -3 aoxidizes the preparation method of sub- silicon composite, feature according to claim 1
It is, in S2, the mass ratio of the phenolic resin in graphene oxide and material A is 1-1.5:2-5.
5. modified carbon coating described in any one of -4 aoxidizes the preparation method of sub- silicon composite, feature according to claim 1
It is, in S2, the size for aoxidizing sub- Si powder is 1-10 μm.
6. modified carbon coating described in any one of -5 aoxidizes the preparation method of sub- silicon composite, feature according to claim 1
It is, in S2, for heating stirring to during being evaporated, temperature is 60-120 DEG C;Vacuum drying temperature is 80-150 DEG C, very
The sky dry time is 12-24h.
7. modified carbon coating described in any one of -6 aoxidizes the preparation method of sub- silicon composite, feature according to claim 1
It is, in S3, the concrete technology of the carbonization treatment is:In the atmosphere of inert gas, with the heating speed of 2-10 DEG C/min
Rate is warming up to 600-1000 DEG C, constant temperature 2-6h;Preferably, the inert gas is one of nitrogen, argon gas or two kinds
Mixture;Preferably, heating rate is 2 DEG C/min.
8. modified carbon coating described in any one of -7 aoxidizes the preparation method of sub- silicon composite, feature according to claim 1
It is, is aoxidized in sub- silicon composite in obtained modification carbon coating, the mass content of carbon is 1-10wt%.
9. a kind of modified carbon coating aoxidizes sub- silicon composite, which is characterized in that using as described in any one of claim 1-8
The preparation method that modified carbon coating aoxidizes sub- silicon composite is prepared.
10. a kind of modified carbon coating as claimed in claim 9 aoxidizes sub- silicon composite as lithium ion battery negative material
Using.
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