CN111403740A - Preparation method of silica ink composite material - Google Patents
Preparation method of silica ink composite material Download PDFInfo
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- CN111403740A CN111403740A CN202010210687.7A CN202010210687A CN111403740A CN 111403740 A CN111403740 A CN 111403740A CN 202010210687 A CN202010210687 A CN 202010210687A CN 111403740 A CN111403740 A CN 111403740A
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- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims description 73
- 239000000377 silicon dioxide Substances 0.000 title claims description 22
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 42
- 239000010439 graphite Substances 0.000 claims abstract description 42
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 53
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 39
- 238000001816 cooling Methods 0.000 claims description 31
- 239000010703 silicon Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 22
- 229910052710 silicon Inorganic materials 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 21
- 239000011863 silicon-based powder Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 14
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 229910021382 natural graphite Inorganic materials 0.000 claims description 9
- 229920000620 organic polymer Polymers 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 239000011163 secondary particle Substances 0.000 claims description 7
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 5
- 239000010426 asphalt Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 3
- 239000000498 cooling water Substances 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- 239000011331 needle coke Substances 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052744 lithium Inorganic materials 0.000 abstract description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 9
- 238000009830 intercalation Methods 0.000 abstract description 5
- 230000002687 intercalation Effects 0.000 abstract description 5
- 239000002210 silicon-based material Substances 0.000 abstract description 5
- 239000013543 active substance Substances 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 239000007773 negative electrode material Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000007599 discharging Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- -1 graphite compound Chemical class 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000011887 silicon containing negative electrode material Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000010902 jet-milling Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 238000009489 vacuum treatment Methods 0.000 description 1
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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
- H01M4/38—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
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a preparation method of a silica-graphite composite material, which relates to the technical field of batteries, can obviously improve the expansion characteristic of a silicon-based material, can be used as a negative active substance to be applied to a lithium ion battery system, and has higher lithium intercalation capacity and good cycle stability.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a preparation method of a negative electrode material, and specifically relates to a preparation method of a silica ink composite material.
Background
As is known, a lithium ion battery is a reusable secondary battery having unique advantages as an energy conversion device. With the continuous progress of science and technology and the continuous innovation of lithium ion battery technology, various lithium ion batteries in the market have more excellent service performance, and are widely applied. At present, lithium ion batteries are seen everywhere in life and work of people, but along with increasingly fierce competition, the requirements of people on the living standard are continuously improved, and the requirements on the performance of the lithium ion batteries are also increasingly strict.
The lithium ion battery electrode performance directly affects the comprehensive performance of the battery to a great extent, for example, the capacity of an electrode active material is directly related to the energy density of the battery, and in order to meet the market demand and improve the competitiveness of the product, people continuously develop a novel electrode material with excellent application performance. In addition to the conventional graphite cathode, the research and application of silicon-based materials have been greatly advanced in recent years. Since silicon has ultrahigh theoretical lithium storage capacity (4200 mAh/g), the silicon-containing negative electrode material generally has higher theoretical gram capacity than graphite (372 mAh/g), and the energy density of a cell can be effectively improved.
In the application process, the silicon-based negative electrode material shows higher capacity, but also exposes some disadvantages, such as low efficiency, poor electrode stability and the like, so in recent years, researchers make great efforts in improving the comprehensive performance of the silicon-containing negative electrode material, and also obtain certain results.
Therefore, how to provide a preparation method of silica ink composite material is a long-term technical appeal for the technical personnel in the field.
Disclosure of Invention
In order to overcome the defects in the background technology, the invention provides a preparation method of a silica-ink composite material, which can obviously improve the expansion characteristic of a silicon-based material, can be used as a negative active material to be applied to a lithium ion battery system, and has higher lithium intercalation capacity and good cycle stability.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a preparation method of a silica ink composite material specifically comprises the following steps:
firstly, crushing graphite or needle coke to obtain primary graphite powder with the particle size of 1-5 um as a matrix of a subsequent material;
secondly, mixing silicon powder and silicon dioxide powder by a wet method, pressing, uniformly placing the pressed mixture on a tray in a vacuum high-temperature furnace, placing crushed graphite fragments in a cooling mechanism of the vacuum high-temperature furnace, vacuumizing the vacuum high-temperature furnace, heating the vacuum high-temperature furnace, replacing by using inert gas to ensure the vacuum and inert environment in a cavity of the vacuum high-temperature furnace, heating at a speed of 5-20 ℃/min, heating the heater in the vacuum high-temperature furnace to 1000-1500 ℃, keeping the temperature constant for 2-20 hours, and sublimating the silicon powder and the silicon dioxide powder in the reaction process and reacting to generate SiOx (X is more than 0 and less than 2);
thirdly, the SiOx obtained in the previous step is introduced into a cooling mechanism with graphite fragments in a gas form, the temperature of the cooling mechanism is adjusted to desublimate the SiOx gas, and the SiOx gas is deposited on the surface of a graphite carrier and in particle gaps to obtain a silicon-oxygen/graphite composite material;
fourthly, mixing the obtained silica/graphite composite material with an organic polymer, putting the mixture into a reaction device, heating the mixture in a protective atmosphere at a heating speed of 5-20 ℃/min to 200-1000 ℃, and keeping the temperature for 2-20 hours to uniformly heat the silica/graphite composite material and the organic polymer to obtain secondary particles;
and fifthly, crushing and grading the obtained secondary particles to obtain the silicon/graphite composite material with D50 of 10-30 um.
According to the preparation method of the silica ink composite material, the graphite in the first step is natural graphite or artificial graphite, and preferably natural graphite.
According to the preparation method of the silica ink composite material, in the second step, the silicon powder is micron silicon powder.
In the preparation method of the silica ink composite material, the silicon dioxide powder in the second step is nano silicon dioxide powder.
According to the preparation method of the silica ink composite material, the ratio of the silicon powder to the silicon dioxide powder in the second step is 0.5-2.0 by adopting a molar ratio.
In the preparation method of the silica ink composite material, the vacuum degree of the vacuum heating furnace in the second step is less than or equal to 50 Pa.
According to the preparation method of the silica-graphite composite material, in the second step, the vacuum high-temperature furnace comprises a heater, a vacuum valve, a cooling mechanism and a tray, the heater is arranged in a closed cavity, the tray is arranged in the heater, a mixture of silicon powder and silicon dioxide powder is arranged on the tray, the cooling mechanism is connected to the right side of the cavity, graphite fragments are placed in the cooling mechanism, and the vacuum valve is arranged at the lower part of the left side of the cavity.
According to the preparation method of the silica ink composite material, the cooling mechanism is of a closed structure and is connected with the cavity through a pipeline.
In the preparation method of the silica ink composite material, the cooling mechanism in the third step is cooled by cooling water, and the cooling temperature is 200-800 ℃.
In the preparation method of the silica ink composite material, the organic polymer in the fourth step is asphalt.
By adopting the technical scheme, the invention has the following advantages:
the silicon-based material can obviously improve the expansion characteristic of the silicon-based material, can be used as a negative active material to be applied to a lithium ion battery system, has higher lithium intercalation capacity and good cycle stability, has simple process and low synthesis cost, can controllably prepare a silicon-oxygen/graphite compound by controlling conditions in the synthesis process, relieves the expansion of silicon in the charging and discharging process because the silicon is uniformly deposited on the surface of the graphite in the synthesis process, obtains excellent cycle performance, and is suitable for large-scale popularization and application.
Drawings
FIG. 1 is a schematic view of a vacuum high-temperature furnace according to the present invention;
FIG. 2 is a schematic representation of the results of XRD testing of a silicon/graphite composite;
fig. 3 is data for a silicon/graphite button cell;
FIG. 4 is silicon/graphite cycle performance data;
in the figure: 1. a heater; 2. a vacuum valve; 3. a cooling mechanism; 4. a tray.
Detailed Description
The present invention will be explained in more detail by the following examples, which are not intended to limit the invention;
the preparation method of the silica ink composite material specifically comprises the following steps:
firstly, crushing graphite or needle coke to obtain primary graphite powder with the particle size of 1-5 um as a matrix of a subsequent material; the graphite is natural graphite or artificial graphite, preferably natural graphite, and because most of pores exist in the natural graphite, the deposition area can be increased, and more silicon-based negative electrode materials can be deposited; if the selected graphite does not meet the requirements, the graphite needs to be treated by high-energy grinding or jet milling and other modes in the early stage;
secondly, mixing micron silicon powder and nano silicon dioxide powder by a wet method, pressing by a press, wherein the proportion of the silicon powder to the silicon dioxide powder adopts a molar ratio, the ratio is 0.5-2.0, then uniformly placing the mixture formed by pressing on a tray 4 in a vacuum high-temperature furnace, placing the crushed graphite fragments in a cooling mechanism 3 of the vacuum high-temperature furnace, wherein the placing amount of the graphite fragments is determined according to the volume of the vacuum high-temperature furnace, and is generally 1/5-1/2 collection cavity volume; then, the vacuum high-temperature furnace is vacuumized and then heated, the vacuum degree of the vacuum heating furnace is less than or equal to 50Pa, in order to ensure the vacuum and inert environment in the cavity of the vacuum high-temperature furnace, inert gas is adopted for replacement, preferably nitrogen or argon, the temperature is raised at 5-20 ℃/min, the temperature of a heater 1 in the vacuum high-temperature furnace is raised to 1000-1500 ℃ and then kept constant, the constant temperature is kept for 2-20 hours, and silicon powder and silicon dioxide powder are sublimated and react to generate SiOx (X is more than 0 and less than 2) in the reaction process; as shown in fig. 1, the vacuum high-temperature furnace comprises a heater 1, a vacuum valve 2, a cooling mechanism 3 and a tray 4, wherein the heater 1 is arranged in a closed cavity, the tray 4 is arranged in the heater 1, a mixture of silicon powder and silicon dioxide powder is arranged on the tray 4, the right side of the cavity is connected with the cooling mechanism 3, the cooling mechanism 3 is of a closed structure, the cooling mechanism 3 is connected with the cavity through a pipeline, graphite fragments are placed in the cooling mechanism 3, and the vacuum valve 2 is arranged at the lower part of the left side of the cavity;
thirdly, the SiOx obtained in the previous step is introduced into a cooling mechanism 3 with graphite fragments in a gas form, the cooling mechanism 3 is cooled by cooling water, the cooling temperature is 200-800 ℃, the temperature of the cooling mechanism 3 is adjusted to desublimate the SiOx gas, and the SiOx gas is deposited on the surface of a graphite carrier and in particle gaps to obtain a silicon-oxygen/graphite composite material; in the implementation, the sublimation gas of the inert gas, the reactant and the product in the vacuum high-temperature furnace is required to be kept in the preparation process, no other impurity gas is generated, and the condensation temperature of the gas is controlled within the range of 500-1000 ℃;
fourthly, mixing the obtained silica/graphite composite material with an organic polymer, wherein the organic polymer is asphalt, putting the mixture into a reaction device, heating the mixture in a protective atmosphere at a heating speed of 5-20 ℃/min to 200-1000 ℃, keeping the temperature for 2-20 hours, uniformly heating the silica/graphite composite material and the organic polymer to obtain secondary particles, and simultaneously carrying out a carbon coating layer on the surface of silicon to a certain extent;
and fifthly, crushing and grading the obtained secondary particles to obtain the silicon/graphite composite material with D50 of 10-30 um.
The prepared material is subjected to electrode preparation, a scraper is used for uniformly coating the mixture of AM, SP, CMC and SBR according to a certain proportion on a copper foil current collector, then an electrode piece is obtained by vacuum baking, the electrode piece is prepared through cutting and rolling processes, a button cell is prepared by the electrode piece and metal lithium, the electrochemical performance characterization is carried out, the electrolyte adopts 1.0 Mol/L L iPF6, the solvent composition is EC, EMC =3:7, and 5% of FEC is added into the electrolyte to serve as a film forming additive.
Further, the battery was subjected to 0.1C discharge to 0.005V and then 0.05C discharge to 0.005V to obtain a first lithium intercalation capacity, and charged to 1.5V with 0.1C to obtain a first lithium deintercalation capacity.
First efficiency = first delithiation capacity/first lithium insertion capacity × 100%
And meanwhile, carrying out cycle performance test on the battery and analyzing the electrochemical performance.
Compared with the prior art, the invention has the advantages that:
compared with the prior art, the preparation method of the silicon/graphite cathode material provided by the invention has the advantages that the process is simple, the synthesis cost is low, the silicon-oxygen/graphite compound can be controllably prepared by controlling the conditions in the synthesis process, and the obtained material has good electrochemical performance.
The specific embodiment of the invention is as follows:
1. preparing raw materials: crushing natural graphite, wherein the median particle size of crushed natural graphite is 2um, and subsequent experiments are carried out;
2. mixing silicon and silicon dioxide according to a molar ratio of 1:1, and pressing by a press machine to obtain a mixed block;
3. heating treatment: graphite is placed in a cooling mechanism 3 of a vacuum heating furnace, a silicon source is placed on a tray in a heater, the vacuum heating furnace is subjected to heating vacuum treatment, the vacuum degree is less than or equal to 50Pa, and the temperature in the furnace is 1350 ℃; heating for 10h, and collecting silicon oxide at a condensation end to obtain a silicon/graphite precursor;
4. coating: performing asphalt coating on the silicon/graphite precursor to obtain secondary particles, wherein the coating temperature is 600 ℃, and the coating time is 5 hours;
5. and (3) crushing and grading the coated product to obtain the composite material with D50 being 15um, and performing electrochemical performance characterization.
In the invention, the structural characteristics of the material are shown in FIG. 2, and the obtained material mainly comprises silicon and graphite, because the silicon content is low, the main structure is a graphite diffraction peak;
FIG. 3 shows the first charging and discharging curve of the material, and the first lithium intercalation is 574.9mAh/g and the first lithium deintercalation is 502.6mAh/g according to the test data; the efficiency of the material was 87.4%;
FIG. 4 shows the cycle performance test results of the material, and it can be known from the test results that the material has excellent electrochemical performance after 20 weeks of cycle, and the capacity retention rate is 99.8%;
the invention relates to a simple silicon/graphite composite negative electrode material, which has excellent structural characteristics, and meanwhile, the silicon/graphite negative electrode can be controllably prepared by optimizing parameters in the synthesis process, and because silicon is uniformly deposited on the surface of graphite in the synthesis process, the silicon is relieved from expanding in the charging and discharging processes, and excellent cycle performance is obtained.
The present invention is not described in detail in the prior art.
The embodiments selected for the purpose of disclosing the invention, are presently considered to be suitable, it being understood, however, that the invention is intended to cover all variations and modifications of the embodiments which fall within the spirit and scope of the invention.
Claims (10)
1. A preparation method of a silica ink composite material is characterized by comprising the following steps: the preparation method specifically comprises the following steps:
firstly, crushing graphite or needle coke to obtain primary graphite powder with the particle size of 1-5 um as a matrix of a subsequent material;
secondly, mixing silicon powder and silicon dioxide powder by a wet method, pressing, uniformly placing a pressed mixture on a tray (4) in a vacuum high-temperature furnace, placing crushed graphite fragments in a cooling mechanism (3) of the vacuum high-temperature furnace, vacuumizing the vacuum high-temperature furnace, heating the vacuum high-temperature furnace, replacing the graphite fragments by inert gas to ensure the vacuum and inert environment in a cavity of the vacuum high-temperature furnace, heating at the speed of 5-20 ℃/min, heating a heater (1) in the vacuum high-temperature furnace to 1000-1500 ℃, keeping the temperature constant for 2-20 hours, sublimating the silicon powder and the silicon dioxide powder in the reaction process, and reacting to generate SiOx (X is more than 0 and less than 2);
thirdly, the SiOx obtained in the previous step is introduced into a cooling mechanism (3) with graphite fragments in a gas form, the temperature of the cooling mechanism (3) is adjusted to desublimate the SiOx gas, and the SiOx gas is deposited on the surface of a graphite carrier and in particle gaps to obtain a silicon-oxygen/graphite composite material;
fourthly, mixing the obtained silica/graphite composite material with an organic polymer, putting the mixture into a reaction device, heating the mixture in a protective atmosphere at a heating speed of 5-20 ℃/min to 200-1000 ℃, and keeping the temperature for 2-20 hours to uniformly heat the silica/graphite composite material and the organic polymer to obtain secondary particles;
and fifthly, crushing and grading the obtained secondary particles to obtain the silicon/graphite composite material with D50 of 10-30 um.
2. The method of preparing a silica-ink composite material as claimed in claim 1, wherein: the graphite in the first step is natural graphite or artificial graphite, and preferably natural graphite.
3. The method of preparing a silica-ink composite material as claimed in claim 1, wherein: and in the second step, the silicon powder is micron silicon powder.
4. The method of preparing a silica-ink composite material as claimed in claim 1, wherein: and in the second step, the silicon dioxide powder is nano silicon dioxide powder.
5. The method of preparing a silica-ink composite material as claimed in claim 1, wherein: and the proportion of the silicon powder and the silicon dioxide powder in the second step adopts a molar ratio of 0.5-2.0.
6. The method of preparing a silica-ink composite material as claimed in claim 1, wherein: the vacuum degree of the vacuum heating furnace in the second step is less than or equal to 50 Pa.
7. The method of preparing a silica-ink composite material as claimed in claim 1, wherein: the vacuum high-temperature furnace comprises a heater (1), a vacuum valve (2), a cooling mechanism (3) and a tray (4), wherein the heater (1) is arranged in a closed cavity, the tray (4) is arranged in the heater (1), a mixture of silicon powder and silicon dioxide powder is arranged on the tray (4), the cooling mechanism (3) is connected to the right side of the cavity, graphite fragments are placed in the cooling mechanism (3), and the vacuum valve (2) is arranged on the lower portion of the left side of the cavity.
8. The method of preparing a silica-ink composite material as claimed in claim 7, wherein: the cooling mechanism (3) is of a closed structure, and the cooling mechanism (3) is connected with the cavity through a pipeline.
9. The method of preparing a silica-ink composite material as claimed in claim 1, wherein: and in the third step, the cooling mechanism (3) is cooled by cooling water, and the cooling temperature is 200-800 ℃.
10. The method of preparing a silica-ink composite material as claimed in claim 1, wherein: in the fourth step, the organic polymer is asphalt.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115472809A (en) * | 2022-10-26 | 2022-12-13 | 晖阳(贵州)新能源材料有限公司 | Preparation method of graphite composite material with high first-time efficiency |
| CN115810741A (en) * | 2021-12-28 | 2023-03-17 | 宁德时代新能源科技股份有限公司 | Negative electrode active material, preparation method thereof, and related secondary battery and device |
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Application publication date: 20200710 |