CN114975922A - Small-particle-size nano silicon-carbon negative electrode material and preparation method thereof - Google Patents
Small-particle-size nano silicon-carbon negative electrode material and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000007773 negative electrode material Substances 0.000 title claims description 14
- 239000007833 carbon precursor Substances 0.000 claims abstract description 54
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 49
- 239000010703 silicon Substances 0.000 claims abstract description 46
- 239000000463 material Substances 0.000 claims abstract description 44
- 238000000576 coating method Methods 0.000 claims abstract description 43
- 239000011248 coating agent Substances 0.000 claims abstract description 42
- 239000002131 composite material Substances 0.000 claims abstract description 28
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 21
- 239000010405 anode material Substances 0.000 claims abstract description 17
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- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000012216 screening Methods 0.000 claims abstract description 6
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- 239000005543 nano-size silicon particle Substances 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 19
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 12
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 12
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- 229920001568 phenolic resin Polymers 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
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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
-
- 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
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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
-
- 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
-
- 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
Abstract
The invention discloses a small-particle-size nano silicon-carbon anode material and a preparation method thereof, and the small-particle-size nano silicon-carbon anode material comprises the following specific steps: firstly, coating a carbon precursor material on a flexible substrate and drying to form a film; then placing the film coated with the carbon precursor in PVD coating equipment for coating a silicon film; continuously coating a carbon precursor material on the silicon film, rolling, and repeating the steps to form a carbon precursor silicon composite film; and then placing the sample in an inert atmosphere for calcining and crushing, placing the material in a CVD furnace for gas phase carbon coating, introducing mixed gas for heat preservation reaction, and screening and demagnetizing the CVD coated material. The small-particle-size gas-phase dispersed silicon and carbon precursor composite technology provided by the invention realizes uniform composite of carbon and nanoscale or even sub-nanoscale silicon, and complete and uniform coating of the whole secondary particles is realized through subsequent solid-phase or gas-phase carbon coating, so that the performance of a silicon-carbon cathode material is improved.
Description
Technical Field
The invention belongs to the technical field of preparation of lithium battery cathode materials, and particularly relates to a small-particle-size nano silicon-carbon cathode material and a preparation method thereof.
Background
With the progress of new energy lithium battery technology, batteries are developing in the directions of weight reduction, miniaturization and long endurance, and therefore extremely high requirements are made on the energy density of the batteries. The traditional graphite cathode material is closer to the theoretical capacity of 372mAh/g, and the silicon-based cathode material has higher capacity compared with the traditional graphite cathode material and is the core material of the current high-energy density battery. However, the huge volume change of the silicon-based negative electrode material in the charging and discharging process brings great challenges to the industrial application of the silicon-carbon negative electrode. How to reduce the expansion of the silicon-carbon cathode material and improve the cycle performance of the battery becomes a hot problem of current research.
At present, the silicon-carbon negative electrode material preparation technology is mainly to compound a nano silicon material and a carbon material, and generally the nano silicon material is prepared firstly and then is compounded with a carbon precursor material to prepare a silicon-carbon composite material. In order to alleviate the problems of huge volume change and cycle deterioration of silicon in the process of lithium extraction, the silicon material needs to be nano-sized. Theoretically, the smaller the size of nano-silicon, the better the expansion performance, and the poorer the oxidation resistance and dispersibility. The main means of the current silicon nanocrystallization is a sand milling method and a gas phase cracking method. The nano silicon prepared by the preparation method independently has larger grain diameter or serious agglomeration, and has poorer compounding effect with carbon, thereby bringing great difficulty to the preparation of the silicon-carbon cathode material. The conventional silicon-carbon material is prepared by compounding nano silicon with a carbon material of more than 100 nm. Although the method can meet the commercial application to a certain extent, the problems of less mixing amount, low capacity matching and larger expansion in the actual use process still face.
Disclosure of Invention
The invention aims to provide a preparation method of a small-particle-size nano silicon-carbon negative electrode material, which is used for compounding gas-phase dispersed silicon with small particle size with a carbon precursor to realize uniform compounding of carbon and nanoscale or even sub-nanoscale silicon, so that the performance of the silicon-carbon negative electrode material is improved.
The invention also aims to provide the small-particle-size nano silicon-carbon negative electrode material.
The invention adopts the technical scheme that the preparation method of the small-particle-size nano silicon-carbon anode material is implemented according to the following steps:
s1, coating the carbon precursor material on a flexible substrate and drying to form a uniform film;
s2, placing the film coated with the carbon precursor in PVD coating equipment, and uniformly coating a layer of silicon film;
s3, continuously coating a layer of carbon precursor material on the silicon film and rolling to obtain a carbon precursor silicon composite film;
s4, repeating the steps S2-S3 to form a carbon precursor silicon composite film with a certain thickness;
s5, placing the carbon precursor silicon composite film sample containing the substrate in an inert atmosphere calcining furnace for calcining;
s6, crushing the calcined material until D50 is 3-10 mu m;
s7, placing the crushed material in a CVD furnace for gas phase carbon coating, introducing mixed gas of acetylene and nitrogen, and preserving heat for 1-5 hours at 500-700 ℃;
s8, screening and demagnetizing the material coated by the CVD to obtain the small-particle-size nano silicon-carbon negative electrode material.
The present invention is also characterized in that,
in step S1, the flexible substrate material is any one of PP, PET, PI, PE, PC, and PMMA; the carbon precursor material is any one of phenolic resin, epoxy resin, asphalt and glucose.
In step S2, the silicon thin film has a thickness of not more than 50 nm.
In step S4, the thickness of the carbon precursor silicon composite film is 100-8000 μm.
In step S5, the calcination temperature is 400-600 ℃, and the calcination time is 1-5 h.
In the step S7, the volume ratio of acetylene to nitrogen in the mixed gas is 0.2-1: 1.
the invention adopts another technical scheme that the small-particle-size nano silicon-carbon anode material is prepared by adopting the preparation method.
The invention has the beneficial effects that: the small-particle-size gas-phase dispersed silicon and carbon precursor composite technology provided by the invention realizes uniform composite of precursor carbon and nanoscale or even sub-nanoscale silicon, and complete and uniform coating of the whole secondary particles is realized through subsequent solid-phase or gas-phase carbon coating, so that the performance of the silicon-carbon cathode material is improved. Because the compounding of the nano silicon and the carbon is carried out under the vacuum condition, the compounding uniformity is ensured, and the nano silicon-carbon composite material has good safety during the compounding of the nano silicon-carbon.
Drawings
FIG. 1 is a flow chart of the preparation of the small-particle-size nano silicon-carbon anode material of the invention;
FIG. 2 is a first surface topography of the small-particle-size nano-silicon-carbon anode material of the present invention;
FIG. 3 is a surface topography of the small-particle-size nano silicon carbon anode material of the invention;
FIG. 4 is a third surface topography of the small-particle-size nano silicon carbon anode material of the present invention.
Detailed Description
The invention relates to a preparation method of a small-particle-size nano silicon-carbon anode material, which comprises the following steps of preparing a silicon-carbon composite precursor film as shown in figure 1: preparing a carbon precursor film on a flexible substrate by a coating process, depositing nano silicon on the film by adopting deposition modes such as magnetron sputtering, thermal evaporation and the like, so as to alternately reciprocate to obtain a silicon-carbon composite precursor film with a certain thickness, compacting the film layer by a rolling mode, and realizing close contact between the nano silicon and precursor carbon; the second step is that: calcining the film layer into carbon: the film layer is placed in an inert atmosphere furnace for high-temperature calcination, so that the nano silicon and the carbon are fixed, and certain compaction resistance of particles is ensured; the third step: crushing the calcined material to a certain particle size to obtain silicon-carbon powder; the fourth step: and coating the silicon-carbon powder for the second time to obtain the finished silicon-carbon material.
The method is implemented according to the following steps:
s1, coating the carbon precursor material on a flexible substrate and drying to form a uniform film;
the flexible substrate material is any one of PP, PET, PI, PE, PC and PMMA;
the carbon precursor material is any one of phenolic resin, epoxy resin, asphalt and glucose;
s2, placing the film coated with the carbon precursor in PVD coating equipment, and uniformly coating a layer of silicon film;
wherein, the PVD coating film can be any one of magnetron sputtering coating film, resistance type thermal evaporation coating film and electron beam thermal evaporation coating film;
the thickness of the silicon film is less than 50 nm;
s3, continuously coating a layer of carbon precursor material on the silicon film and rolling to obtain a carbon precursor silicon composite film;
s4, repeating the steps S2-S3 to form a carbon precursor silicon composite film with a certain thickness;
the thickness of the carbon precursor silicon composite film is 100-8000 mu m;
s5, placing the carbon precursor silicon composite film sample containing the substrate in an inert atmosphere calcining furnace for calcining;
the calcining temperature is 400-600 ℃, and the calcining time is 1-5 h.
S6, crushing the calcined material until D50 is 3-10 mu m;
the pulverization can be mechanical pulverization or air flow pulverization;
s7, placing the crushed material in a CVD furnace for gas phase carbon coating, introducing mixed gas of acetylene and nitrogen, and preserving heat for 1-5 hours at 500-700 ℃;
the volume ratio of acetylene to nitrogen in the mixed gas is 0.2-1;
s8, screening and demagnetizing the material coated by the CVD to obtain the nano silicon carbon negative electrode material with small particle size.
The independently prepared nano silicon has larger grain diameter, more serious agglomeration and poorer effect when being compounded with carbon, so that the performance of the silicon-carbon cathode material still cannot achieve large-scale application. The invention provides a small-particle-size gas-phase dispersed silicon and carbon precursor compounding technology, so that uniform compounding of carbon and nanoscale or even sub-nanoscale silicon is realized, complete and uniform coating of the nano silicon is realized through subsequent gas-phase or solid-phase carbon coating, and the performance of a silicon-carbon cathode material is improved. Because the compounding of the nano silicon and the carbon is carried out simultaneously under the vacuum condition, the compounding uniformity is ensured, and the nano silicon composite material has good safety during nano compounding, thereby overcoming the danger of the traditional process for preparing the nano silicon by cracking the silane.
Example 1
S1, coating the phenolic carbon precursor material on a flexible substrate PP, and drying to form a uniform film;
s2, placing the film coated with the phenolic resin carbon precursor in a magnetron sputtering system, and uniformly plating a silicon film with the thickness of 50 nm;
s3, continuously coating a layer of phenolic carbon precursor material on the film obtained in the step S2, and rolling to obtain a carbon precursor silicon composite film, wherein the thickness of the phenolic carbon precursor film is 0.5 mu m;
s4, repeating S2-S3 to form a carbon precursor silicon composite film with a certain thickness, wherein the thickness of the composite film is 500 mu m;
s5, placing the film coating sample containing the substrate in an inert atmosphere calcining furnace for calcining, wherein the calcining temperature is controlled at 500 ℃, and the calcining time is 2 hours;
s6, crushing the calcined material until D50 is 8 mu m;
s7, placing the crushed material in a CVD furnace for gas phase coating, introducing mixed gas of acetylene and nitrogen, and preserving heat for 2 hours at 700 ℃;
the volume ratio of acetylene to nitrogen in the mixed gas is 0.2: 1;
and S8, screening and demagnetizing the material coated by the CVD to obtain the small-particle-size silicon-carbon negative electrode material.
Example 2
S1, coating the pitch carbon precursor material on a flexible substrate PET, and drying to form a uniform film;
s2, placing the film coated with the pitch carbon precursor in an electron beam evaporation system, and uniformly plating a silicon film with the thickness of 30 nm;
s3, continuously coating a layer of pitch carbon precursor material on the film obtained in the step S2, and rolling to obtain a carbon precursor silicon composite film, wherein the thickness of the pitch carbon precursor film is 1 mu m;
s4, repeating S2-S3 to form the pitch carbon precursor silicon composite film with a certain thickness, wherein the thickness of the composite film is 1000 mu m;
s5, placing the film coating sample containing the substrate in an inert atmosphere calcining furnace for calcining, wherein the calcining temperature is controlled at 600 ℃, and the calcining time is 2 hours;
s6, crushing the calcined material until D50 is 9 μm;
s7, placing the crushed material in a CVD furnace for gas phase coating, introducing mixed gas of acetylene and nitrogen, and preserving heat for 2 hours at 600 ℃;
the volume ratio of acetylene to nitrogen in the mixed gas is 0.5: 1.
example 3
The invention relates to a preparation method of a small-particle-size nano silicon-carbon anode material, which is implemented according to the following steps:
s1, coating the epoxy resin carbon precursor material on PC and drying to form a uniform film;
s2, placing the film coated with the carbon precursor in PVD coating equipment, and uniformly coating a layer of silicon film;
the thickness of the silicon film is 20 nm;
s3, continuously coating a layer of epoxy resin carbon precursor material on the silicon film and rolling to obtain a carbon precursor silicon composite film, wherein the thickness of the carbon precursor is 0.3 mu m;
s4, repeating the steps S2-S3 to form a carbon precursor silicon composite film with a certain thickness; the thickness of the carbon precursor silicon composite film is 500 mu m;
s5, placing the carbon precursor silicon composite film sample containing the substrate in an inert atmosphere calcining furnace for calcining; the calcining temperature is 500 ℃, and the calcining time is 3 h.
S6, crushing the calcined material until D50 is 8 mu m;
s7, placing the crushed material in a CVD furnace for gas phase carbon coating, introducing mixed gas of acetylene and nitrogen, and preserving heat for 4 hours at 650 ℃;
the volume ratio of acetylene to nitrogen in the mixed gas is 0.2: 1;
s8, screening and demagnetizing the material coated by the CVD to obtain the small-particle-size nano silicon-carbon negative electrode material.
Table 1 properties of nano silicon carbon anode materials prepared in examples 1-3
| Examples | Capacity of | First effect | Cycle performance |
| Example 1 | 1800mAh/g | 90％ | 400ycle@95％ |
| Example 2 | 1500mAh/g | 91％ | 500ycle@95％ |
| Example 3 | 2000mAh/g | 91.5％ | 200cycle@97％ |
The performance of the nano silicon carbon anode material prepared in the embodiments 1 to 3 is shown in table 1, as the nano silicon prepared by the present invention is performed under a vacuum condition, the problem of oxidation during the preparation of the nano silicon is effectively avoided, and thus the prepared nano silicon carbon material has a first effect of more than 90% and a high capacity exertion. Meanwhile, the graphite is matched to 450mAh/g for cylindrical battery cycle test, and the cylindrical battery has excellent cycle performance.
Fig. 2-4 are surface topography diagrams of the small-particle-size nano silicon carbon anode material, from which it can be clearly seen that the coated secondary particle silicon carbon surface carbon layer is uniform, compact and complete, no nano silicon is exposed, the particle size is about 10 μm, and is generally smaller than the particle size of 13-20 μm in the industry. The particle size has an important influence on the rate capability of the material, and generally, the smaller the particle size, the better the rate capability.
Claims (7)
1. The preparation method of the small-particle-size nano silicon-carbon negative electrode material is characterized by comprising the following steps of:
s1, coating the carbon precursor material on a flexible substrate and drying to form a uniform film;
s2, placing the film coated with the carbon precursor in PVD coating equipment, and uniformly coating a layer of silicon film;
s3, continuously coating a layer of carbon precursor material on the silicon film and rolling to obtain a carbon precursor silicon composite film;
s4, repeating the steps S2-S3 to form a carbon precursor silicon composite film with a certain thickness;
s5, placing the carbon precursor silicon composite film sample containing the substrate in an inert atmosphere calcining furnace for calcining;
s6, crushing the calcined material until D50 is 3-10 mu m;
s7, placing the crushed material in a CVD furnace for gas phase carbon coating, introducing mixed gas of acetylene and nitrogen, and preserving heat for 1-5 hours at 500-700 ℃;
s8, screening and demagnetizing the material coated by the CVD to obtain the small-particle-size nano silicon-carbon negative electrode material.
2. The method for preparing small-particle-size nano silicon carbon anode material according to claim 1, wherein in the step S1, the flexible substrate material is any one of PP, PET, PI, PE, PC and PMMA; the carbon precursor material is any one of phenolic resin, epoxy resin, asphalt and glucose.
3. The method as claimed in claim 1, wherein in step S2, the thickness of the silicon thin film is not greater than 50 nm.
4. The method for preparing a small-particle-size nano silicon-carbon anode material according to claim 1, wherein in the step S4, the thickness of the carbon precursor silicon composite film is 100-8000 μm.
5. The method for preparing the small-particle-size nano silicon-carbon anode material as claimed in claim 1, wherein in the step S5, the calcination temperature is 400-600 ℃, and the calcination time is 1-5 h.
6. The method for preparing small-particle-size nano silicon-carbon anode material according to claim 1, wherein in the step S7, the volume ratio of acetylene to nitrogen in the mixed gas is 0.2-1: 1.
7. a small-particle-size nano silicon-carbon negative electrode material is characterized by being prepared by the preparation method of any one of claims 1 to 6.
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