CN114583148B - Preparation method of silicon oxide-based graphite composite anode material for lithium ion battery - Google Patents
Preparation method of silicon oxide-based graphite composite anode material for lithium ion battery Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 83
- 239000010439 graphite Substances 0.000 title claims abstract description 83
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 33
- 239000002131 composite material Substances 0.000 title claims abstract description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910052814 silicon oxide Inorganic materials 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000010405 anode material Substances 0.000 title claims description 22
- 238000003756 stirring Methods 0.000 claims abstract description 116
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims abstract description 73
- 239000000843 powder Substances 0.000 claims abstract description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000007787 solid Substances 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 238000001694 spray drying Methods 0.000 claims abstract description 16
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 15
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims abstract description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000012046 mixed solvent Substances 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 8
- 239000007773 negative electrode material Substances 0.000 claims abstract description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 74
- 238000010438 heat treatment Methods 0.000 claims description 47
- 239000000203 mixture Substances 0.000 claims description 30
- 238000001816 cooling Methods 0.000 claims description 28
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 24
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 22
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 20
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 20
- 239000011240 wet gel Substances 0.000 claims description 20
- 239000000499 gel Substances 0.000 claims description 19
- 229920000877 Melamine resin Polymers 0.000 claims description 13
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 13
- 239000004327 boric acid Substances 0.000 claims description 13
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 229910052786 argon Inorganic materials 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 11
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 10
- 239000008098 formaldehyde solution Substances 0.000 claims description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 10
- 238000005245 sintering Methods 0.000 claims description 9
- 238000007323 disproportionation reaction Methods 0.000 claims description 7
- 230000000630 rising effect Effects 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims 1
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- 230000000052 comparative effect Effects 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000009831 deintercalation Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910016569 AlF 3 Inorganic materials 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- DGXAGETVRDOQFP-UHFFFAOYSA-N 2,6-dihydroxybenzaldehyde Chemical compound OC1=CC=CC(O)=C1C=O DGXAGETVRDOQFP-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
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- 230000000670 limiting effect 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
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- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
-
- 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
-
- 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)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of lithium ion batteries, in particular to a preparation method of a silicon oxide-based graphite composite negative electrode material for a lithium ion battery, which comprises the steps of adding aluminum trifluoride into a mixed solvent, stirring until the aluminum trifluoride is uniformly dispersed, adding SiO x powder, spray-drying to obtain pre-coated SiO x powder, adding the pre-coated SiO x powder into water, performing ultrasonic dispersion for 10-20min to obtain solution C, adding polyethylene glycol into water, mixing and stirring until clarification to obtain solution D, adding the solution D into the solution C, stirring, adding graphite gel powder, continuously stirring, centrifuging, washing the solid, drying the solid, and roasting under nitrogen protection.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a preparation method of a silicon oxide-based graphite composite anode material for a lithium ion battery.
Background
In recent years, the lithium ion battery technology is rapidly developed, and the lithium ion battery technology is widely applied to the fields of portable electronic equipment, new energy automobiles, power energy storage and the like, and breaks through the bottleneck of the existing electrode materials, so that the lithium ion battery technology is a key for developing the lithium ion battery with high capacity and long service life. The negative electrode material is a carrier of lithium ions and electrons, plays roles in storing and releasing energy, and is an important component of the battery. Thus, the electrochemical properties of the negative electrode material also determine, to some extent, the performance of the battery.
Silicon is widely focused due to the advantages of high theoretical capacity, low working potential, rich reserves and the like, but the silicon still has the defects of poor conductivity, huge volume change in the lithium intercalation and deintercalation process and the like when being used as a cathode material.
Disclosure of Invention
The invention aims to: aiming at the technical problems, the invention provides a preparation method of a silicon oxide-based graphite composite anode material for a lithium ion battery.
The technical scheme adopted is as follows:
The preparation method of the silicon oxide-based graphite composite anode material for the lithium ion battery comprises the following steps:
S1: mixing resorcinol and formaldehyde solution, stirring until the mixture is clear, adding sodium carbonate, continuously stirring to obtain solution A, adding melamine and boric acid into water, preserving heat at 75-85 ℃ for 30-50min, cooling to obtain solution B, adding solution A into solution B, stirring for 20-40min, adding graphite, preserving heat at 75-85 ℃ for 30-50min, heating to 90-95 ℃ for reacting for 36-48h to obtain graphite wet gel, drying and grinding to obtain graphite gel powder;
s2: under the protection of argon, heating the SiO to 1000-1050 ℃ for disproportionation treatment for 3-5 hours, and then cooling along with a furnace to obtain SiO x powder;
s3: adding aluminum trifluoride into a mixed solvent composed of isopropanol and water, stirring until the mixture is uniformly dispersed, adding SiO x powder, continuously stirring, and then spray-drying to obtain pre-coated SiO x powder;
s4: adding pre-coated SiO x powder into water, performing ultrasonic dispersion for 10-20min to obtain a solution C, adding polyethylene glycol into water, mixing and stirring until the mixture is clarified to obtain a solution D, adding the solution D into the solution C, stirring the mixed solution at 60-70 ℃ for 2-3h, adding graphite gel powder, continuously stirring for 2-3h, centrifuging, washing the obtained solid, drying, and roasting at 800-900 ℃ for 2-4h under the protection of nitrogen.
Further, the mass ratio of melamine to boric acid in S1 is 2.4-2.6:1.
Further, the addition amount of graphite in S1 is 5-10% of the sum of the mass of the solution A and the mass of the solution B.
Further, the temperature rising speed in the disproportionation treatment of the SiO in the S2 is 10-15 ℃/min.
Further, the volume ratio of isopropanol to water in S3 is 1:10-15.
Further, the mass ratio of aluminum trifluoride to SiO x powder in S3 is 1:50-100.
Further, in the step S3, the temperature of an air inlet is 180-200 ℃ and the temperature of a discharge outlet is 60-80 ℃ during spray drying.
Further, the mass ratio of the pre-coated SiO x powder to the graphite gel powder in S4 is 1:4-6.
Further, the pre-sintering is carried out before the roasting in the step S4, the pre-sintering temperature is 300-350 ℃, and the pre-sintering time is 1-2h.
Further, the temperature rising speed during presintering is 10-15 ℃/min, and the temperature rising speed during roasting is 2-5 ℃/min.
The invention has the beneficial effects that:
Along with the repeated Li + insertion/extraction actions, the volume change of the fully lithiated SiO material is not negligible, the continuous 'breathing phenomenon' of SiO can lead to cracking, pulverization and even falling of the electrode material, the reversible capacity of the battery is rapidly attenuated, the conductivity of SiO is low, the actual multiplying power characteristic of the battery can be seriously influenced under the condition of high-current charge and discharge, aiming at the defects, the SiO is converted into SiO x through disproportionation reaction to improve the content of inactive substances, a method for constructing proper electrode composition is feasible, the conductivity and mechanical property of graphite are better, the second phase is the best composite phase with the SiO x material, in the invention, resorcinol-formaldehyde is used as a carbon source, melamine is used as a nitrogen source, boric acid is used as a boron source, the prepared graphite gel has a stable cross-linked network, and has high mechanical strength and thermal stability, the carbonized carbon residue is high, the surface wettability is good, the electrochemical resistance of SiO x is reduced by AlF 3 pre-coating, the electrochemical performance under high multiplying power is improved, and the electrolyte is easily combined with F - in electrolyte in the circulating process, so that a good ion conductor AlF 4 - is formed, the quick intercalation and deintercalation of Li + is possible, meanwhile, the contact area between SiO x particles and electrolyte is favorably reduced by the multi-layer coating structure formed by baking AlF 3 and polyethylene glycol, a stable solid-phase electrolyte interface film is formed, meanwhile, the addition of graphite gel plays the roles of bridging and coating each SiO x particle, thereby improving the conductivity of the whole electrode, inhibiting the volume change in the lithium intercalation and deintercalation process, the first charge specific capacity reaches more than 1300mAh/g, the first charge and discharge efficiency is about 90%, and the capacity retention rate can reach more than 81% after 100 times of circulation.
Detailed Description
The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1:
a preparation method of a silicon oxide-based graphite composite anode material for a lithium ion battery comprises the following steps:
Mixing and stirring 16g of resorcinol and 40mL of 30wt% formaldehyde solution until the mixture is clear, adding 0.08g of sodium carbonate, continuing to stir to obtain solution A, adding 4.8g of melamine and 2g of boric acid into 50mL of water, preserving heat at 85 ℃ for 50min, cooling to obtain solution B, adding the solution A into the solution B, stirring for 40min, adding 10g of graphite, preserving heat at 85 ℃ for 50min, heating to 95 ℃ for reaction for 48h to obtain graphite wet gel, drying and grinding the graphite wet gel, obtaining graphite gel powder, heating 100g of SiO to 1050 ℃ at a speed of 15 ℃/min under argon protection, cooling with a furnace to obtain SiO x powder, adding 1g of aluminum trifluoride into a mixed solvent consisting of isopropanol (20 mL) and water (280 mL), stirring until the mixture is uniformly dispersed, adding 60g of SiO x powder, continuing to stir, performing spray drying, performing ultrasonic dispersion at an air inlet temperature of 200 ℃ for 80 ℃ for 50min, obtaining pre-coated SiO x powder, heating 2g of pre-coated SiO x, adding 200mL of water for ultrasonic dispersion for 20 ℃ for 20min, performing water-stirring for 40 h, adding the obtained solid to obtain a mixed solution, stirring for 10 h, stirring for 3h, heating to obtain a mixed solution, heating to obtain a dry solution, heating to obtain a mixed solution, heating for 300mL of carbon black powder, stirring for 10g, stirring for 3h, stirring, and stirring for stirring until the solid is obtained after heating is finished, and cooling is finished, and the mixed solution is subjected to 20mL, and is subjected to heating to cooling.
Example 2:
a preparation method of a silicon oxide-based graphite composite anode material for a lithium ion battery comprises the following steps:
Mixing and stirring 16g of resorcinol and 40mL of 30wt% formaldehyde solution until the mixture is clear, adding 0.08g of sodium carbonate, continuing stirring to obtain solution A, adding 4.8g of melamine and 2g of boric acid into 50mL of water, preserving heat at 75 ℃ for 30min, cooling to obtain solution B, adding the solution A into the solution B, stirring for 20min, adding 10g of graphite, preserving heat at 75 ℃ for stirring for 30min, heating to 90 ℃ for reaction for 36-48h to obtain graphite wet gel, drying and grinding the graphite wet gel to obtain graphite gel powder, heating 100g of SiO to 1000 ℃ at a speed of 10 ℃/min under argon protection, cooling with a furnace to obtain SiO x powder, adding 1g of aluminum trifluoride into a mixed solvent consisting of isopropanol (20 mL) and water (280 mL), stirring until the SiO x powder is uniformly dispersed, continuing stirring and then spray-drying, adding the obtained solution into the mixed solvent, stirring for 2g of SiO x powder, adding 2g of the obtained pre-coated SiO x into 200mL of water, conducting ultrasonic dispersion for 10mL of graphite C at a speed of 200 ℃ for 10mL, heating for 10 h, conducting water-washing for 2h, stirring for obtaining solid, adding the obtained solid, stirring for 10g of carbon dioxide, stirring for 10 h, stirring, and stirring for 2h, and stirring.
Example 3:
a preparation method of a silicon oxide-based graphite composite anode material for a lithium ion battery comprises the following steps:
Mixing and stirring 16g of resorcinol and 40mL of 30wt% formaldehyde solution until the mixture is clear, adding 0.08g of sodium carbonate, continuing to stir to obtain solution A, adding 4.8g of melamine and 2g of boric acid into 50mL of water, preserving heat at 75 ℃ for 50min, cooling to obtain solution B, adding the solution A into the solution B, stirring for 20min, adding 10g of graphite, preserving heat at 85 ℃ for stirring for 30min, heating to 95 ℃ for reaction for 36h to obtain graphite wet gel, drying and grinding the graphite wet gel, obtaining graphite gel powder, heating 100g of SiO to 1000 ℃ at a speed of 15 ℃/min under the protection of argon, cooling with a furnace to obtain SiO x powder, adding 1g of aluminum trifluoride into a mixed solvent consisting of isopropanol (20 mL) and water (280 mL), stirring until the mixture is uniformly dispersed, adding 60g of SiO x powder, continuing to stir, then spray-drying, adding the mixture into the spray-drying, wherein the air inlet temperature is 180 ℃, the temperature is 80 ℃, preserving heat at 85 ℃, pre-coating SiO x, heating 2g of pre-coating SiO x mL of water is added into 200mL of water, ultrasonic dispersion for 10mL of C for 10 h, grinding after drying, obtaining graphite gel powder is obtained after the mixture is heated for 10 h, heating at a speed of 300 h, stirring for 10g of water, stirring until the mixture is clear solution is obtained after heating is mixed, heating is finished, heating to obtain 100g of SiO x h, stirring, adding the solid powder after heating is mixed solution after heating to 10g of water, stirring, and stirring is continuously at a speed of 10g of water, namely, and stirring for 10g of water, and stirring.
Example 4:
a preparation method of a silicon oxide-based graphite composite anode material for a lithium ion battery comprises the following steps:
Mixing and stirring 16g of resorcinol and 40mL of 30wt% formaldehyde solution until the mixture is clear, adding 0.08g of sodium carbonate, continuing to stir to obtain solution A, adding 4.8g of melamine and 2g of boric acid into 50mL of water, preserving heat at 85 ℃ for 30min, cooling to obtain solution B, adding the solution A into the solution B, stirring for 40min, adding 10g of graphite, preserving heat at 75 ℃ for 50min, heating to 90 ℃ for reaction for 48h to obtain graphite wet gel, drying and grinding the graphite wet gel, obtaining graphite gel powder, heating 100g of SiO to 1050 ℃ at a speed of 10 ℃/min under argon protection, cooling with a furnace to obtain SiO x powder, adding 1g of aluminum trifluoride into a mixed solvent consisting of isopropanol (20 mL) and water (280 mL), stirring until the mixture is uniformly dispersed, adding 60g of SiO x powder, continuing to stir, performing spray drying, performing ultrasonic dispersion at an air inlet temperature of 200 ℃ for 60 ℃, obtaining pre-coated SiO x, heating 2g of pre-coated SiO x, performing ultrasonic dispersion for 20mL of the graphite wet gel, performing water for 20mL, performing water-washing for 2h, heating for 20mL, stirring for 2h, adding the obtained solid, stirring for 2h, stirring for obtaining a mixed solution after heating to obtain a mixed solution, stirring for 300mL of carbon black powder, adding the solid, stirring for 2g of carbon black, stirring for 2mL, stirring for 2h, and stirring for obtaining the solid, and stirring.
Example 5:
a preparation method of a silicon oxide-based graphite composite anode material for a lithium ion battery comprises the following steps:
Mixing and stirring 16g resorcinol and 40mL of 30wt% formaldehyde solution until the mixture is clear, adding 0.08g sodium carbonate, continuing to stir to obtain solution A, adding 4.8g melamine and 2g boric acid into 50mL of water, preserving heat at 85 ℃ for 50min, cooling to obtain solution B, adding the solution A into the solution B, stirring for 40min, adding 10g graphite, preserving heat and stirring for 50min at 85 ℃, heating to 95 ℃ for reaction for 48h to obtain graphite wet gel, drying and grinding the graphite wet gel to obtain graphite gel powder, heating 100g SiO to 1050 ℃ at a speed of 15 ℃/min under argon protection, cooling with a furnace to obtain SiO x powder, adding 1g aluminum trifluoride into a mixed solvent consisting of isopropanol (20 mL) and water (280 mL), stirring until the mixture is uniformly dispersed, adding 60g SiO x powder, continuing to stir, then spray-drying, carrying out air inlet temperature at 200 ℃, discharging port temperature at 80 ℃, obtaining pre-coated SiO x powder, adding 2g pre-coated SiO x mL SiO powder into water for ultrasonic dispersion for 200mL, carrying out ultrasonic dispersion for 20mL, carrying out heat treatment for 5h, cooling with the furnace cooling for cooling to obtain solid under the condition, adding the mixed solution, stirring for 10g, stirring for 3h, stirring until the solid is obtained after the solid is mixed solution is mixed, adding into the solution is subjected to stirring for 3h, stirring, namely, stirring, adding into the solution after heating for 20mL, stirring, and stirring for obtaining the solid solution after heating.
Comparative example 1
Comparative example 1 is substantially the same as example 1 except that graphite powder of the same particle diameter is used instead of graphite gel powder.
A preparation method of a silicon oxide-based graphite composite anode material for a lithium ion battery comprises the following steps:
Under the protection of argon, heating 100g of SiO to 1050 ℃ at a speed of 15 ℃/min for disproportionation treatment for 5 hours, cooling with a furnace to obtain SiO x powder, adding 1g of aluminum trifluoride into a mixed solvent consisting of isopropanol (20 mL) and water (280 mL), stirring until the mixture is uniformly dispersed, adding 60g of SiO x powder, continuously stirring, spray drying, wherein the temperature of an air inlet is 200 ℃, the temperature of a discharge outlet is 80 ℃ during spray drying to obtain pre-coated SiO x powder, adding 2g of pre-coated SiO x powder into 200mL of water for ultrasonic dispersion for 20 minutes to obtain solution C, adding 40g of polyethylene glycol into 300mL of water, mixing and stirring until the mixture is clarified to obtain solution D, adding the solution D into the solution C, stirring the mixed solution for 3 hours at 70 ℃, adding 10g of graphite powder, continuously stirring for 3 hours, centrifuging, washing the obtained solid, drying after water washing, heating to 350 ℃ at a speed of 15 ℃/min under the protection of nitrogen, pre-sintering for 2 hours, and heating to 900 ℃ for 4 hours.
Comparative example 2
Comparative example 2 is substantially the same as example 1 except that SiO x powder is replaced with SiO of the same particle size.
A preparation method of a silicon oxide-based graphite composite anode material for a lithium ion battery comprises the following steps:
Mixing and stirring 16g resorcinol and 40mL 30wt% formaldehyde solution until the mixture is clear, adding 0.08g sodium carbonate, continuing to stir to obtain solution A, adding 4.8g melamine and 2g boric acid into 50mL water, preserving heat at 85 ℃ for 50min, cooling to obtain solution B, adding the solution A into the solution B, stirring for 40min, adding 10g graphite, preserving heat at 85 ℃ for 50min, heating to 95 ℃ for reacting for 48h to obtain graphite wet gel, drying and grinding the graphite wet gel to obtain graphite gel powder, adding 1g aluminum trifluoride into a mixed solvent consisting of isopropanol (20 mL) and water (280 mL), stirring until the mixture is uniformly dispersed, adding 60g SiO powder, continuing to stir and then spray-drying, wherein the air inlet temperature is 200 ℃ and the discharge outlet temperature is 80 ℃, cooling to obtain solution B, adding 2g pre-coated SiO powder into 200mL water, carrying out ultrasonic dispersion for 20min, adding 40g polyethylene glycol into 300mL water, mixing and stirring to obtain solution D, adding the solution D into the solution C, mixing and stirring for 3 ℃ for 3h, heating to the graphite wet gel after drying for 3h, and continuously stirring at a speed of 2 ℃ for 4h, namely, carrying out water-washing, and drying, namely, and further stirring until the solid is protected by the solid is obtained after the mixture is washed by water, and the mixture is heated for 15 h.
Comparative example 3
Comparative example 3 is substantially the same as example 1 except that the pretreatment was not performed.
A preparation method of a silicon oxide-based graphite composite anode material for a lithium ion battery comprises the following steps:
Mixing and stirring 16g of resorcinol and 40mL of 30wt% formaldehyde solution until the mixture is clear, adding 0.08g of sodium carbonate, continuing stirring to obtain solution A, adding 4.8g of melamine and 2g of boric acid into 50mL of water, preserving heat at 85 ℃ for 50min, cooling to obtain solution B, adding solution A into solution B, stirring for 40min, adding 10g of graphite, preserving heat at 85 ℃ for 50min, heating to 95 ℃ for reacting for 48h to obtain graphite wet gel, drying and grinding the graphite wet gel, obtaining graphite gel powder, under the protection of argon, heating 100g of SiO to 1050 ℃ at a speed of 15 ℃/min, carrying out disproportionation treatment for 5h, cooling with a furnace to obtain SiO x powder, adding 2g of SiO x powder into 200mL of water, carrying out ultrasonic dispersion for 20min, obtaining solution C, adding 40g of polyethylene glycol into 300mL of water, mixing and stirring until the solution B is clear, adding solution D into solution C, stirring for 3h at 70 ℃, adding 10g of graphite, stirring for 3h, centrifuging, washing the obtained graphite gel with water, drying at 15 ℃ for 5 ℃ for 2h at a speed of 50 ℃ after nitrogen protection, and baking at a speed of 900 ℃ for 2 h.
Comparative example 4
Comparative example 4 is substantially the same as example 1 except that polyethylene glycol treatment was not performed.
A preparation method of a silicon oxide-based graphite composite anode material for a lithium ion battery comprises the following steps:
Mixing and stirring 16g of resorcinol and 40mL of 30wt% formaldehyde solution until the mixture is clear, adding 0.08g of sodium carbonate, continuing stirring to obtain solution A, adding 4.8g of melamine and 2g of boric acid into 50mL of water, preserving heat at 85 ℃ for 50min, cooling to obtain solution B, adding the solution A into the solution B, stirring for 40min, adding 10g of graphite, preserving heat at 85 ℃ for 50min, heating to 95 ℃ for reacting for 48h to obtain graphite wet gel, drying and grinding the graphite wet gel to obtain graphite gel powder, heating 100g of SiO to 1050 ℃ at a speed of 15 ℃/min under argon protection, cooling with a furnace to obtain SiO x powder, adding 1g of aluminum trifluoride into a mixed solvent consisting of isopropanol (20 mL) and water (280 mL), stirring until the mixture is uniformly dispersed, adding 60g of SiO x powder, continuing stirring, then spray-drying, adding the mixture into the spray-drying solution at an air inlet temperature of 200 ℃ and a discharge outlet temperature of 80 ℃, obtaining pre-coated SiO x powder, adding 2g of pre-coated SiO x into 200mL of water, conducting ultrasonic dispersion for 20 ℃ for 20min, carrying out heat treatment for 5h, cooling with a furnace cooling to obtain solid powder, adding the solid powder after the pre-drying for 2g of the pre-coated SiO powder, stirring for 2h at a speed of 900 ℃ for 20min, stirring, and continuously heating until the solid is dried for 2h, and stirring.
Performance test:
Weighing and uniformly mixing the silicon oxide-based graphite composite anode materials prepared in the embodiments 1-5 and the comparative examples 1-4 with superconductive carbon and polyacrylic acid according to the mass ratio of 8:1:1, wherein the polyacrylic acid is mixed in the form of a solution with the mass content of 10%, stirring the mixture into slurry, coating the slurry on copper foil, drying, cutting to obtain a pole piece, placing the pole piece into a glove box, taking a metal lithium piece as a counter electrode, adopting a polypropylene diaphragm, adopting a LiPF 6/EC+DEC+EMC solution with the mass ratio of 1mol/L as electrolyte, wherein EC is ethylene carbonate, DEC is diethyl carbonate, EMC is methyl ethyl carbonate, and the volume ratio of the three is 1:1:1, a CR2032 type button cell was assembled in a glove box filled with dry argon.
The battery performance test was performed at 25±2 ℃ as follows:
(1) 0.1C is discharged to 0.005V; (2) standing for 1min; (3) 0.05C to 0.005V; (4) standing for 1min; (5) 0.02C discharge to 0.005V; (6) standing for 1min; (7) 0.1C to 3.0V; (8) Standing for 1min, and circulating for 100 times according to the steps, wherein the battery performance test results of the silicon oxide-based graphite composite anode materials in examples 1-5 and comparative examples 1-4 are shown in Table 1:
Table 1:
As shown in the table 1, the lithium ion battery prepared from the silicon oxide-based graphite composite anode material has excellent electrochemical performance, the initial charge specific capacity reaches more than 1300mAh/g, the initial charge and discharge efficiency is about 90%, and the capacity retention rate can reach more than 81% after 100 times of circulation.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The preparation method of the silicon oxide-based graphite composite anode material for the lithium ion battery is characterized by comprising the following steps of:
S1: mixing resorcinol and formaldehyde solution, stirring until the mixture is clear, adding sodium carbonate, continuously stirring to obtain solution A, adding melamine and boric acid into water, preserving heat at 75-85 ℃ for 30-50min, cooling to obtain solution B, adding solution A into solution B, stirring for 20-40min, adding graphite, preserving heat at 75-85 ℃ for 30-50min, heating to 90-95 ℃ for reacting for 36-48h to obtain graphite wet gel, drying and grinding to obtain graphite gel powder;
s2: under the protection of argon, heating the SiO to 1000-1050 ℃ for disproportionation treatment for 3-5 hours, and then cooling along with a furnace to obtain SiO x powder;
s3: adding aluminum trifluoride into a mixed solvent composed of isopropanol and water, stirring until the mixture is uniformly dispersed, adding SiO x powder, continuously stirring, and then spray-drying to obtain pre-coated SiO x powder;
s4: adding pre-coated SiO x powder into water, performing ultrasonic dispersion for 10-20min to obtain a solution C, adding polyethylene glycol into water, mixing and stirring until the mixture is clarified to obtain a solution D, adding the solution D into the solution C, stirring the mixed solution at 60-70 ℃ for 2-3h, adding graphite gel powder, continuously stirring for 2-3h, centrifuging, washing the obtained solid, drying, and roasting at 800-900 ℃ for 2-4h under the protection of nitrogen.
2. The method for preparing the silicon oxide-based graphite composite anode material for the lithium ion battery according to claim 1, wherein the mass ratio of melamine to boric acid in S1 is 2.4-2.6:1.
3. The method for preparing a silicon oxide-based graphite composite negative electrode material for a lithium ion battery according to claim 1, wherein the addition amount of graphite in S1 is 5-10% of the sum of the mass of the solution A and the mass of the solution B.
4. The method for preparing a silicon oxide-based graphite composite negative electrode material for a lithium ion battery according to claim 1, wherein the heating rate in the disproportionation treatment of SiO in S2 is 10-15 ℃/min.
5. The method for preparing a silicon oxide-based graphite composite anode material for a lithium ion battery according to claim 1, wherein the volume ratio of isopropanol to water in S3 is 1:10-15.
6. The method for preparing a silicon oxide-based graphite composite anode material for a lithium ion battery according to claim 1, wherein the mass ratio of aluminum trifluoride to SiO x powder in S3 is 1:50-100.
7. The method for preparing a silicon oxide-based graphite composite negative electrode material for a lithium ion battery according to claim 1, wherein the temperature of an air inlet is 180-200 ℃ and the temperature of a discharge outlet is 60-80 ℃ during spray drying in the step S3.
8. The preparation method of the silicon oxide-based graphite composite anode material for the lithium ion battery as claimed in claim 1, wherein the mass ratio of the pre-coated SiO x powder to the graphite gel powder in S4 is 1:4-6.
9. The method for preparing a silicon oxide-based graphite composite negative electrode material for a lithium ion battery according to claim 1, wherein the pre-sintering is performed before the calcination in the step S4, the pre-sintering temperature is 300-350 ℃, and the pre-sintering time is 1-2h.
10. The method for preparing a silicon oxide-based graphite composite negative electrode material for a lithium ion battery according to claim 9, wherein the temperature rising speed during pre-sintering is 10-15 ℃/min, and the temperature rising speed during sintering is 2-5 ℃/min.
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