CN113422016A - Silicon-carbon negative electrode material for lithium ion battery and preparation method thereof - Google Patents
Silicon-carbon negative electrode material for lithium ion battery and preparation method thereof Download PDFInfo
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- CN113422016A CN113422016A CN202110663855.2A CN202110663855A CN113422016A CN 113422016 A CN113422016 A CN 113422016A CN 202110663855 A CN202110663855 A CN 202110663855A CN 113422016 A CN113422016 A CN 113422016A
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 23
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 22
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 60
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 33
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000001035 drying Methods 0.000 claims abstract description 25
- 238000000197 pyrolysis Methods 0.000 claims abstract description 24
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 23
- 239000013067 intermediate product Substances 0.000 claims abstract description 20
- 239000000047 product Substances 0.000 claims abstract description 20
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 19
- 239000011259 mixed solution Substances 0.000 claims abstract description 16
- 239000004020 conductor Substances 0.000 claims abstract description 11
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims abstract description 5
- 238000005507 spraying Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 20
- 239000011230 binding agent Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 7
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- 241001330002 Bambuseae Species 0.000 claims description 7
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- 239000000835 fiber Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 239000002028 Biomass Substances 0.000 claims description 6
- 239000002033 PVDF binder Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- 235000017060 Arachis glabrata Nutrition 0.000 claims description 4
- 244000105624 Arachis hypogaea Species 0.000 claims description 4
- 235000010777 Arachis hypogaea Nutrition 0.000 claims description 4
- 235000018262 Arachis monticola Nutrition 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 235000020232 peanut Nutrition 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
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- 235000010413 sodium alginate Nutrition 0.000 claims description 3
- 229940005550 sodium alginate Drugs 0.000 claims description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- 229920000858 Cyclodextrin Polymers 0.000 claims description 2
- 241000196324 Embryophyta Species 0.000 claims description 2
- 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 2
- 229920002472 Starch Polymers 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 2
- 239000006230 acetylene black Substances 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 239000010902 straw Substances 0.000 claims description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
Abstract
The invention belongs to the technical field of lithium ion batteries, and discloses a silicon-carbon negative electrode material for a lithium ion battery and a preparation method thereof. (1) Uniformly stirring and mixing the organic carbon source 1, the conductive material and water, then adding the nano silicon powder, and uniformly dispersing to obtain a first mixed solution; (2) drying the first mixed solution, and then carrying out high-temperature pyrolysis in an inert atmosphere to obtain an intermediate product 1; (3) dissolving aminopropyltriethoxysilane in ethanol, and uniformly spraying the solution on the surface of the intermediate product 1 to obtain an intermediate product 2; (4) dispersing graphene oxide in ethanol, and uniformly stirring the graphene oxide and the intermediate product 2 to obtain a second mixed solution; and drying the second mixed solution, and then carrying out high-temperature pyrolysis in an inert atmosphere to obtain a target product. According to the invention, before the graphene layer is coated, the carbon material is partially coated on the surface of the nano silicon powder, and meanwhile, the conductive material is added into the carbon material, so that the internal conductivity of the composite material is improved.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a silicon-carbon negative electrode material for a lithium ion battery and a preparation method thereof.
Background
The silicon has the highest specific capacity (4200 mAh/g) and a moderate voltage platform (0.4V vs Li/Li +), meets the requirements of high specific capacity and good safety performance as a negative electrode material, and is one of the potential choices for upgrading and updating the negative electrode of the lithium ion battery. However, silicon as a negative electrode material has low self conductivity, and has large volume change in the charging and discharging processes, and the generated mechanical stress can cause the material to be pulverized and lose electrical contact, so that the cycle performance of the battery is rapidly reduced.
Therefore, a method for improving poor cycle performance of silicon materials in lithium batteries is urgently needed to be developed.
Disclosure of Invention
The invention aims to provide a silicon-carbon negative electrode material for a lithium ion battery and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a silicon-carbon negative electrode material for a lithium ion battery comprises the following steps:
(1) uniformly stirring and mixing an organic carbon source 1, a conductive material and water according to the mass ratio of 1: 0.2-0.3: 1-2, then adding nano silicon powder, wherein the mass ratio of the organic carbon source 1 to the nano silicon powder is 1: 1-3, and uniformly dispersing to obtain a first mixed solution;
(2) drying the first mixed solution, and then carrying out high-temperature pyrolysis reaction in an inert atmosphere to obtain an intermediate product 1;
(3) dissolving aminopropyltriethoxysilane in ethanol, and uniformly spraying the solution on the surface of the intermediate product 1 to obtain an intermediate product 2; the mass ratio of the aminopropyltriethoxysilane to the organic carbon source 1 is (0.01-0.1) to 1;
(4) dispersing graphene oxide in ethanol, and uniformly stirring the graphene oxide and the intermediate product 2 to obtain a second mixed solution; the mass ratio of the graphene oxide to the nano silicon powder is (0.5-1) to 1;
(5) and drying the second mixed solution, and then carrying out high-temperature pyrolysis reaction in an inert atmosphere to obtain a target product 1.
Preferably, the organic carbon source 1 is at least one of glucose, sucrose, cyclodextrin, soluble starch, cellulose, polyvinyl alcohol, polyvinylidene fluoride and phenolic resin; the conductive material is at least one of carbon nano tube, acetylene black, conductive carbon black and graphite.
Preferably, the diameter of the nano silicon powder is 100-300 nm.
Preferably, the drying temperature in the step (2) is 60-100 ℃, and the drying time is 2-8 h; the drying temperature in the step (5) is 40-50 ℃, and the drying time is 1-2 h.
Preferably, the high-temperature pyrolysis reaction temperature in the step (2) and the step (5) is 600-900 ℃, and the time is 1.5-4 h.
Preferably, after the step (5) is finished, the obtained target product 1 is subjected to a step (6), namely, the organic carbon source 2 and the binder are dispersed in ethanol, the target product 1 is added and uniformly dispersed, then the drying is carried out, and the high-temperature pyrolysis reaction is carried out in an inert atmosphere to obtain the target product 2.
Preferably, the mass ratio of the organic carbon source 2 to the nano silicon powder is (1-2) to 1; the mass ratio of the organic carbon source 2 to the binder is 1: 0.1-0.5.
Preferably, the organic carbon source 2 is plant fiber powder obtained by directly crushing biomass raw materials, and the biomass raw materials are at least one of bamboo shoot shells, straws, bamboo scraps and peanut shells; the binder is at least one of polyvinylidene fluoride, polytetrafluoroethylene, styrene butadiene rubber, sodium carboxymethylcellulose or sodium alginate.
Preferably, the high-temperature pyrolysis reaction temperature in the step (6) is 600-.
The silicon-carbon negative electrode material for the lithium ion battery is prepared by the preparation method.
In the present invention, in the step (3), the step (4) and the step (6), the amount and the volume part of ethanol are not required as long as the corresponding substances can be dissolved or dispersed, and 30v% or more of ethanol is preferable.
Has the advantages that:
(1) according to the invention, before coating the graphene layer, the carbon material is partially coated on the surface of the nano silicon powder, so that the agglomeration effect among silicon nano particles is obviously reduced, the dispersion uniformity is good, the direct contact between silicon and electrolyte can be reduced, and meanwhile, the conductive material is added in the carbon material, so that the conductive performance in the composite material is improved;
(2) before the graphene layer is coated, the intermediate product is treated by aminopropyltriethoxysilane, so that the surface of the intermediate product is positively charged, and graphene oxide is negatively charged, therefore, the intermediate product can be uniformly coated by the graphene layer through electrostatic action;
(3) and after the graphene is coated, further modifying the target product by adopting an organic carbon source 2, wherein the biomass fiber powder is adhered to the target product through a binder, and meanwhile, the biomass fiber powder is mutually overlapped and interwoven, and after high-temperature carbonization, a conductive network is formed inside the material, so that the overall conductive performance of the target product is further improved.
Detailed Description
The technical solution of the present invention is further explained in detail with reference to the following examples, but the scope of the present invention is not limited thereto.
Example 1
A preparation method of a silicon-carbon negative electrode material for a lithium ion battery comprises the following steps:
(1) firstly, uniformly stirring and mixing an organic carbon source 1, a conductive material and deionized water according to the mass ratio of 1: 0.2: 2, then adding nano silicon powder, and performing ultrasonic dispersion to obtain a first mixed solution; the organic carbon source 1 is polyvinyl alcohol; the conductive material is carbon black; the diameter of the nano silicon powder is 300 nm, and the mass ratio of the organic carbon source 1 to the nano silicon powder is 1: 1;
(2) drying the first mixed solution at the drying temperature of 100 ℃ for 4 hours, and then putting the dried slurry into a tubular furnace to perform first high-temperature pyrolysis treatment in an inert atmosphere at the pyrolysis temperature of 700 ℃ for 2 hours to obtain an intermediate product 1;
(3) dissolving aminopropyltriethoxysilane in 95v% ethanol, and uniformly spraying the solution on the surface of the intermediate product 1 to obtain an intermediate product 2, wherein the mass ratio of the dosage of the aminopropyltriethoxysilane to the organic carbon source 1 is 0.01: 1;
(4) dispersing graphene oxide in 95v% ethanol, and stirring and mixing the graphene oxide and the intermediate product 2 to obtain a second mixed solution; the mass ratio of the graphene oxide to the nano silicon powder is 0.5: 1;
(5) and drying the second mixed solution at the drying temperature of 50 ℃ for 1 h, and then performing second high-temperature pyrolysis treatment in an inert atmosphere at the pyrolysis temperature of 650 ℃ for 3 h to obtain a target product 1.
Example 2
The difference from example 1 is that: in the step (1), the organic carbon source 1 is polyvinylidene fluoride, the conductive material is graphite, and the mass ratio of the organic carbon source 1 to the conductive material to the deionized water is 1: 0.3: 2; the diameter of the nano silicon powder is 100 nm, and the mass ratio of the organic carbon source 1 to the nano silicon powder is 1: 2; in the step (2), the temperature of the first high-temperature pyrolysis treatment is 800 ℃, and the pyrolysis time is 1.5 h; in the step (3), the mass ratio of the consumption of the aminopropyltriethoxysilane to the organic carbon source 1 is 0.05: 1; in the step (4), the mass ratio of the graphene oxide to the nano silicon powder is 1: 1; otherwise, the same procedure as in example 1 was repeated.
Example 3
The difference from example 1 is that: after step (5) is completed, step (6) is performed: dispersing an organic carbon source 2 and a binder in 95v% ethanol, adding the target product 1 obtained in the step (5) into the ethanol, uniformly dispersing the mixture by ultrasonic waves, drying the mixture to remove the ethanol, wherein the drying temperature is 40 ℃ and the drying time is 2 hours, carrying out high-temperature pyrolysis treatment for the third time in an inert atmosphere, and obtaining a target product 2, wherein the pyrolysis temperature is 750 ℃ and the pyrolysis time is 3 hours; the mass ratio of the organic carbon source 2 to the nano silicon powder is 1.5: 1; the mass ratio of the organic carbon source 2 to the binder is 1: 0.3; the organic carbon source 2 is obtained by crushing peanut shell powder and sieving the crushed peanut shell powder by a sieve of 150 meshes, and the average grain diameter is 150 meshes; the binder is sodium alginate; steps (1) to (5) were the same as in example 1.
Example 4
The difference from example 1 is that: after step (5) is completed, step (6) is performed: dispersing an organic carbon source 2 and a binder in 95v% ethanol, adding the target product 1 obtained in the step (5) into the ethanol, uniformly dispersing the mixture by ultrasonic waves, drying the mixture to remove the ethanol, wherein the drying temperature is 40 ℃ and the drying time is 2 hours, carrying out high-temperature pyrolysis treatment for the third time in an inert atmosphere, and obtaining a target product 2, wherein the pyrolysis temperature is 800 ℃ and the pyrolysis time is 4 hours; the mass ratio of the organic carbon source 2 to the nano silicon powder is 2: 1; the mass ratio of the organic carbon source 2 to the binder is 1: 0.5; the bamboo fiber powder is obtained by directly crushing bamboo shell fibers and screening the bamboo shell fibers with a 100-mesh screen, wherein the average particle size is 100 meshes; the binder is polytetrafluoroethylene; steps (1) to (5) were the same as in example 1.
Comparative example
This example is a comparative example of example 1, and differs from example 1 in that: performing surface treatment on the intermediate product 1 without using aminopropyltriethoxysilane, namely directly performing step (4) to coat graphene oxide after step (2); otherwise, the same procedure as in example 1 was repeated.
The target product 1 prepared in example 1-2, the target product 2 prepared in example 3-4, the comparative target product 1 prepared in comparative example and artificial graphite are mixed according to the mass ratio of 1: 1 to form a negative electrode material for a lithium battery, the negative electrode material for the lithium battery, binders PVDF and carbon black are uniformly mixed according to the mass ratio of 95: 3: 2, the mixture is mixed with deionized water according to the mass ratio of 1: 1.2 to form slurry, the slurry is coated on copper foil, the slurry is cut and weighed to form a negative electrode sheet, then the negative electrode sheet and a lithium sheet pair electrode sheet are assembled to form a lithium ion button cell, and the first effect, gram capacity, cycle performance at 25 ℃ and 45 ℃ of the composite material are tested, and the test results are shown in Table 1. Wherein the discharge current in the cycle test at 25 ℃ and 45 ℃ is 1A.
As can be seen from Table 1: the lithium ion battery prepared by the embodiments of the invention has good cycle performance under normal temperature and high temperature, capacity retention rate reaches the use requirement when the battery is cycled for 100 circles, and capacity and first effect are greatly improved compared with the common graphite.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a silicon-carbon negative electrode material for a lithium ion battery is characterized by comprising the following steps:
(1) uniformly stirring and mixing an organic carbon source 1, a conductive material and water according to the mass ratio of 1: 0.2-0.3: 1-2, then adding nano silicon powder, wherein the mass ratio of the organic carbon source 1 to the nano silicon powder is 1: 1-3, and uniformly dispersing to obtain a first mixed solution;
(2) drying the first mixed solution, and then carrying out high-temperature pyrolysis reaction in an inert atmosphere to obtain an intermediate product 1;
(3) dissolving aminopropyltriethoxysilane in ethanol, and uniformly spraying the solution on the surface of the intermediate product 1 to obtain an intermediate product 2; the mass ratio of the aminopropyltriethoxysilane to the organic carbon source 1 is (0.01-0.1) to 1;
(4) dispersing graphene oxide in ethanol, and uniformly stirring the graphene oxide and the intermediate product 2 to obtain a second mixed solution; the mass ratio of the graphene oxide to the nano silicon powder is (0.5-1) to 1;
(5) and drying the second mixed solution, and then carrying out high-temperature pyrolysis reaction in an inert atmosphere to obtain a target product 1.
2. The method for preparing the silicon-carbon negative electrode material for the lithium ion battery according to claim 1, wherein the method comprises the following steps: the organic carbon source 1 is at least one of glucose, sucrose, cyclodextrin, soluble starch, cellulose, polyvinyl alcohol, polyvinylidene fluoride and phenolic resin; the conductive material is at least one of carbon nano tube, acetylene black, conductive carbon black and graphite.
3. The method for preparing the silicon-carbon negative electrode material for the lithium ion battery according to claim 1, wherein the method comprises the following steps: the diameter of the nano silicon powder is 100-300 nm.
4. The method for preparing the silicon-carbon negative electrode material for the lithium ion battery according to claim 1, wherein the method comprises the following steps: the drying temperature in the step (2) is 60-100 ℃, and the drying time is 2-8 h; the drying temperature in the step (5) is 40-50 ℃, and the drying time is 1-2 h.
5. The method for preparing the silicon-carbon negative electrode material for the lithium ion battery according to claim 1, wherein the method comprises the following steps: the high-temperature pyrolysis reaction temperature in the step (2) and the step (5) is 600-900 ℃, and the time is 1.5-4 h.
6. The method for preparing the silicon-carbon negative electrode material for the lithium ion battery according to claim 1, wherein the method comprises the following steps: and (5) after the step (5) is finished, the obtained target product 1 is subjected to a step (6), namely, the organic carbon source 2 and the binder are dispersed in ethanol, the target product 1 is added and uniformly dispersed, then the mixture is dried, and the high-temperature pyrolysis reaction is carried out in an inert atmosphere to obtain the target product 2.
7. The method for preparing the silicon-carbon negative electrode material for the lithium ion battery according to claim 6, wherein the method comprises the following steps: the mass ratio of the organic carbon source 2 to the nano silicon powder is (1-2) to 1; the mass ratio of the organic carbon source 2 to the binder is 1: 0.1-0.5.
8. The method for preparing the silicon-carbon negative electrode material for the lithium ion battery according to claim 6, wherein the method comprises the following steps: the organic carbon source 2 is plant fiber powder obtained by directly crushing biomass raw materials, and the biomass raw materials are at least one of bamboo shoot shells, straws, bamboo scraps and peanut shells; the binder is at least one of polyvinylidene fluoride, polytetrafluoroethylene, styrene butadiene rubber, sodium carboxymethylcellulose or sodium alginate.
9. The method for preparing the silicon-carbon negative electrode material for the lithium ion battery according to claim 6, wherein the method comprises the following steps: the high-temperature pyrolysis reaction temperature in the step (6) is 600-1000 ℃, and the time is 1.5-6 h.
10. A silicon-carbon negative electrode material for lithium ion batteries prepared by the preparation method according to any one of claims 1 to 9.
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Application publication date: 20210921 |