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 PDF

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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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sub
carbon coating
silicon composite
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aoxidizes
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郭军坡
郑刚
王辉
刘会
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Gotion High Tech Co Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • H01M4/366Composites as layered products
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/38Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386Silicon or alloys based on silicon
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485Selection 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • H01M4/625Carbon or graphite
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

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

A kind of modified carbon coating oxidation sub- silicon composite, preparation method and applications
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.
CN201810620047.6A 2018-06-15 2018-06-15 Modified carbon-coated silicon monoxide composite material, preparation method and application thereof Pending CN108899488A (en)

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CN107403919A (en) * 2017-07-29 2017-11-28 合肥国轩高科动力能源有限公司 Composite material of nitrogen-doped carbon material coated with silicon monoxide and preparation method thereof
CN109817966A (en) * 2019-01-07 2019-05-28 宁波维科电池有限公司 A kind of preparation method of composite cathode material of lithium ion battery
CN110429263A (en) * 2019-08-13 2019-11-08 宁波富理电池材料科技有限公司 A kind of graphene/silicon carbon composite, preparation method and application
CN112736231A (en) * 2021-01-12 2021-04-30 杭州新川新材料有限公司 Preparation method of silicon monoxide negative electrode material of lithium ion battery
CN113816384A (en) * 2021-08-30 2021-12-21 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of phosphorus-doped porous carbon-coated silica material and product thereof
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CN113816384A (en) * 2021-08-30 2021-12-21 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of phosphorus-doped porous carbon-coated silica material and product thereof
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