CN110867562A - Preparation method of lithium battery silicon-carbon composite film cathode - Google Patents
Preparation method of lithium battery silicon-carbon composite film cathode Download PDFInfo
- Publication number
- CN110867562A CN110867562A CN201911130722.8A CN201911130722A CN110867562A CN 110867562 A CN110867562 A CN 110867562A CN 201911130722 A CN201911130722 A CN 201911130722A CN 110867562 A CN110867562 A CN 110867562A
- Authority
- CN
- China
- Prior art keywords
- rollers
- silicon
- film
- group
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002153 silicon-carbon composite material Substances 0.000 title claims abstract description 27
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 62
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 62
- 238000000034 method Methods 0.000 claims abstract description 44
- 238000003763 carbonization Methods 0.000 claims abstract description 34
- 238000005507 spraying Methods 0.000 claims abstract description 30
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 29
- 238000010438 heat treatment Methods 0.000 claims abstract description 27
- 238000001035 drying Methods 0.000 claims abstract description 25
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 22
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 20
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 20
- 238000005096 rolling process Methods 0.000 claims abstract description 19
- 238000005406 washing Methods 0.000 claims abstract description 19
- 230000008569 process Effects 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002131 composite material Substances 0.000 claims abstract description 13
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims abstract description 11
- 235000017557 sodium bicarbonate Nutrition 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 5
- 230000001681 protective effect Effects 0.000 claims abstract description 4
- 238000005520 cutting process Methods 0.000 claims abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 230000007935 neutral effect Effects 0.000 claims description 9
- 229920001721 polyimide Polymers 0.000 claims description 9
- 238000002791 soaking Methods 0.000 claims description 8
- 239000004642 Polyimide Substances 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- XHFLOLLMZOTPSM-UHFFFAOYSA-M sodium;hydrogen carbonate;hydrate Chemical class [OH-].[Na+].OC(O)=O XHFLOLLMZOTPSM-UHFFFAOYSA-M 0.000 claims 2
- 238000005554 pickling Methods 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 22
- 229910052799 carbon Inorganic materials 0.000 abstract description 22
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 9
- 239000000377 silicon dioxide Substances 0.000 abstract description 7
- 238000010000 carbonizing Methods 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 108
- 238000012360 testing method Methods 0.000 description 22
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 20
- 229910052710 silicon Inorganic materials 0.000 description 18
- 239000010703 silicon Substances 0.000 description 18
- 239000007773 negative electrode material Substances 0.000 description 14
- 239000000843 powder Substances 0.000 description 12
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 239000005416 organic matter Substances 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- 239000002931 mesocarbon microbead Substances 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 239000011889 copper foil Substances 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 7
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
- 229910052749 magnesium Inorganic materials 0.000 description 6
- 239000005543 nano-size silicon particle Substances 0.000 description 6
- 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 description 5
- 229930006000 Sucrose Natural products 0.000 description 5
- 239000010406 cathode material Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 229910052814 silicon oxide Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000005720 sucrose Substances 0.000 description 5
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 229910021426 porous silicon Inorganic materials 0.000 description 4
- NCZAACDHEJVCBX-UHFFFAOYSA-N [Si]=O.[C] Chemical compound [Si]=O.[C] NCZAACDHEJVCBX-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920001690 polydopamine Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229960003638 dopamine Drugs 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000007770 graphite material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- -1 silicate ester Chemical class 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 229910003130 ZrOCl2·8H2O Inorganic materials 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 239000007833 carbon precursor Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Images
Classifications
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
-
- 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
- H01M4/62—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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to the field of silicon-carbon composite films, in particular to a preparation method of a silicon-carbon composite film with good cycle performance. A preparation method of a lithium battery silicon-carbon composite film negative electrode comprises the following steps: using a thermoplastic organic film as a raw material, placing the film in a rolling device, sequentially stretching the film by three groups of rollers with the rotating speed ratio of 1: 1.05-1.15: 1.15-1.25, simultaneously spraying ethyl orthosilicate, sodium bicarbonate and ammonia water on the rollers to form a silicon dioxide layer, drying, uniformly spraying a small amount of magnesium powder on the surface of the silicon dioxide layer, folding and cutting the silicon dioxide layer into 3-5 layers, and then performing high-temperature carbonization: keeping the temperature at 195-210 ℃ for 28-36 min, heating to 690-720 ℃, keeping the temperature for 1.9-2.5 h, heating to 995-1100 ℃, carbonizing for 4.8-5.5 h, and taking Ar gas as protective atmosphere; after high-temperature carbonization, the required composite film is obtained after acid washing, water washing and drying in sequence. The invention has simple process, is suitable for large-scale industrial production, and the prepared silicon-embedded carbon film has good cycle performance.
Description
Technical Field
The invention relates to the field of silicon-carbon composite films, in particular to a preparation method of a silicon-carbon composite film with good cycle performance.
Background
With the continuous progress of the lithium battery anode technology, the requirements on accessories such as cathode materials, electrolyte, diaphragms and the like are high, the application of the traditional graphite cathode in the lithium battery cathode is not satisfactory, and the theoretical specific capacity of 372mah/g cannot meet the requirement of a high-capacity lithium battery. In order to solve the problem, the silicon negative electrode material becomes a priority for upgrading and updating the carbon-based negative electrode material due to extremely high theoretical specific capacity, excellent chemical inertness and wide raw material sources. However, lithium intercalation mechanisms of the pure silicon negative electrode and the carbon-based material are different, volume expansion of 300-400% can be generated in the lithium ion deintercalation process, an SEI film can be repeatedly formed in the expansion and contraction processes to cause rapid consumption of lithium ions, the conductivity of silicon is poor, and the application of silicon in the battery negative electrode is greatly influenced. At present, most of the solutions of manufacturers at home and abroad are to compound with other negative electrode materials, including carbon, metal/metal oxide, etc., but the synthesis difficulty is high, and in order to obtain more excellent negative electrode performance, high-cost nano silicon is often used, which are also main reasons for restricting the marketization of silicon negative electrodes. Therefore, the method has very important practical significance for the research on the simplification of the preparation method of the silicon-based negative electrode and the improvement of the cycle performance.
The patent application with the application number of 2019101466088 discloses a preparation method of a silicon-carbon negative electrode material of a lithium ion battery, which comprises the following steps: (1) dissolving nano silicon powder in an ammonia water solution, adding tetraethoxysilane, coating silicon oxide on the surface of silicon nano particles through a polycondensation reaction, cleaning a product with absolute ethyl alcohol, drying and collecting the product for later use; (2) adding the powder obtained in the step (1) into a dopamine solution, introducing oxygen for polymerization under the condition that the pH =8.5 to obtain a silicon-carbon precursor, cleaning the product with distilled water, drying and collecting the product for later use; (3) carbonizing the powder obtained in the step (2) at high temperature under the protection of gas, and cooling to room temperature; and treating the obtained product with hydrofluoric acid, filtering, cleaning to be neutral, and drying to obtain the silicon-carbon negative electrode material. By adopting the method of the invention to carry out hydrolytic polymerization, then cladding and finally carrying out high-temperature carbonization on the nano silicon powder, the internal gap of the nano silicon substrate can be controlled, and the cycle performance of the silicon-based cathode can be effectively improved.
The patent application with the application number of 2018112543948 provides a preparation method of a novel silicon-carbon anode material with a mesoporous structure, which comprises the following steps: p123 and ZrOCl2·8H2O is added toH3PO4Stirring the solution until P123 is completely dissolved, and then adding TEOS to obtain a mixed solution; transferring the mixed solution into a hydrothermal kettle for crystallization, filtering, washing with water, drying, roasting and cooling to obtain a mesoporous molecular sieve; mixing mesoporous molecular sieve with Mg powder, and sintering in a quartz tube; soaking in hydrochloric acid solution to remove impurities, filtering, and drying; then mixing with sucrose, adding deionized water, stirring uniformly and drying; and finally, calcining at high temperature, and cooling to obtain the Si/C cathode material with the novel mesoporous structure. According to the invention, the sucrose pyrolysis coats the surface of the mesoporous silicon, so that energy attenuation can be effectively inhibited, the silicon is separated from electrolyte, the charge-discharge efficiency is improved, the shape of the short mesoporous silicon-carbon anode material prepared by the in-situ hydrothermal method is regular, the agglomeration of silicon nano material particles is effectively reduced, the structure is not easy to collapse, and higher discharge capacity can be maintained.
The patent application with the application number of 2018114497817 discloses a preparation method of a negative electrode material of a lithium ion battery, namely, silicon oxide-carbon/graphite. Taking ethyl orthosilicate as a silicon source and sucrose as a carbon source, compounding gel-state silicon oxide, sucrose and graphite in situ by utilizing hydrolysis-condensation reaction of the ethyl orthosilicate, and dispersing the graphite by ball milling to obtain a uniform silicon-oxygen-sucrose-graphite precursor. And (3) cracking sucrose and reducing silicon oxide in the subsequent heat treatment process, thereby preparing the uniformly-compounded silicon oxide-carbon/graphite material. The in-situ compounding process of the silicon oxide and the graphite has the advantages of simple process and low cost, and the prepared silicon oxide-carbon/graphite material is compounded uniformly. The introduction of the graphite can enhance the electronic conductivity of the composite material and effectively improve the coulombic efficiency of the composite electrode material, thereby obviously improving the electrochemical performance of the electrode material. Can be used as a potential high-performance lithium ion battery cathode material and is expected to be widely applied to the fields of various portable electronic equipment, electric automobiles, aerospace and the like.
The patent application with the application number of 2018113935886 discloses a silicon-carbon negative electrode material based on mesocarbon microbeads and a preparation method thereof. The preparation method mainly comprises the following steps: firstly, carrying out surface modification on the mesocarbon microbeads by using inorganic acid, and coating a layer of nano silicon dioxide particles on the surfaces of the modified mesocarbon microbeads; mixing and carbonizing the silicon dioxide-coated mesocarbon microbeads and a certain mass of asphalt to obtain a silicon dioxide/mesocarbon microbeads/amorphous carbon composite material; reacting the silicon dioxide/mesocarbon microbeads/amorphous carbon composite material with a proper amount of magnesium powder at 500-750 ℃ for 2-7 h, and carrying out acid washing, water washing and drying to obtain the mesocarbon microbead-based silicon-carbon negative electrode material. The silicon-carbon negative electrode material prepared based on the mesocarbon microbeads has excellent lithium battery negative electrode characteristics and is rich in raw material sources.
The patent application with the application number of 2015106758421 discloses a preparation method of a silicon-based negative electrode material for a lithium ion battery, which comprises the steps of preparing a silicon dioxide coated nano aluminum oxide material by using tetraethoxysilane as a silicon source and nano aluminum oxide as a template agent, and then carrying out magnesiothermic reduction and acid treatment to obtain hollow porous silicon; coating a layer of polydopamine on the surface of the hollow porous silicon by utilizing the self-polymerization reaction of the dopamine, and then performing heat treatment to prepare the hollow porous silicon coated with the polydopamine pyrolytic carbon layer, namely the silicon-based negative electrode material for the lithium ion battery. The hollow structure of the porous silicon can provide a certain expansion space for the volume change of the silicon in the charging and discharging processes, and the nitrogen-doped carbon layer formed by heat treatment of the polydopamine has better mechanical property and conductivity than the common carbon layer, so that the silicon-based negative electrode material has better cycle performance and rate capability. After 50 cycles, the charge specific capacity retention rate of the silicon-based negative electrode material is still 90%.
Disclosure of Invention
The invention provides a preparation method of a silicon-carbon composite film negative electrode of a lithium battery, aiming at the problems of complex preparation method and poor cycle performance of the silicon-based negative electrode of the lithium battery at present.
In order to solve the problems, the invention adopts the following technical scheme:
a preparation method of a lithium battery silicon-carbon composite film negative electrode comprises the following steps:
(1) the method comprises the following steps of using a thermoplastic organic film as a raw material, placing the film in rolling equipment for stretching, and spraying ethyl orthosilicate, sodium bicarbonate and ammonia water on rollers, wherein the thermoplastic organic film sequentially passes through three groups of rollers, and the rotating speed ratio of the three groups of rollers is 1: 1.05-1.15: 1.15-1.25;
(2) drying the stretched thermoplastic organic film obtained in the step (1), uniformly spraying a small amount of magnesium powder on the surface of the film, folding and cutting, wherein the number of folded thermoplastic organic films is 3-5;
(3) carrying out high-temperature carbonization on the thermoplastic organic film folded and cut in the step (2), wherein the high-temperature carbonization process comprises the steps of keeping the temperature at 195-210 ℃ for 28-36 min, heating to 690-720 ℃ for 1.9-2.5 h, then heating to 995-1100 ℃ for carbonization for 4.8-5.5 h, and using Ar gas as protective atmosphere;
(4) and (4) carrying out acid washing, water washing and drying on the thermoplastic organic film carbonized at the high temperature in the step (3) to obtain the required composite film.
Experiments show that the thermoplastic organic matter can be better stretched to form a film with a certain pore space by the rotation speed ratio of the three groups of rollers in the step (1) being 1: 1.05-1.15: 1.15-1.25, the tetraethoxysilane, the sodium bicarbonate and the ammonia water can enter the thermoplastic organic matter film, and an electrode cathode material with excellent electrical property can be obtained. If the difference of the rotating speeds of the three groups of rollers is too large, the pores of the thermoplastic organic film are different in size and are not uniformly distributed, the tetraethoxysilane, the sodium bicarbonate and the ammonia water are not uniformly distributed in the thermoplastic organic film or on the surface of the thermoplastic organic film, and the battery prepared from the material is poor in performance after being folded.
Further, the material of the thermoplastic organic film in the step (1) is one of polyimide or polyacrylic acid, and preferably, the material of the thermoplastic organic film is polyimide.
More preferably, the sodium bicarbonate in the step (1) is a supersaturated sodium bicarbonate aqueous solution, and the concentration of ammonia water is 2-5 mol/L.
Through a large number of experiments, when the rotating speed ratio of the three groups of rollers in the step (1) is 1:1.1:1.2, the thermoplastic organic matter can be stretched best to form a film with certain pores, and the tetraethoxysilane, the sodium bicarbonate and the ammonia water can uniformly enter the thermoplastic organic matter film, so that the electrode negative electrode material with excellent electrical property can be obtained, and further preferably, the rotating speed ratio of the three groups of rollers in the step (1) is 1:1.1: 1.2.
Further preferably, in the rolling process in the step (1), the rolling temperature is an organic thin film softening temperature.
Further preferably, the three groups of hot rollers in the step (1) are respectively a first group of rollers, a second group of rollers and a third group of rollers, wherein ethyl orthosilicate is sprayed in front of the first group of rollers, a sodium bicarbonate aqueous solution is sprayed between the first group of rollers and the second group of rollers, and ammonia water is sprayed between the second group of rollers and the third group of rollers; the distance between the first group of rollers is preferably 0.01-0.03 mm, the distance between the second group of rollers is 0.010-0.20 mm, and the distance between the third group of rollers is 0.01-0.02 mm.
The distance between the three groups of rollers has certain influence on the uniformity of the material, the distribution uniformity of the tetraethoxysilane, the sodium bicarbonate and the ammonia water in the thermoplastic organic film is poor when the distance is too long, the uneven material is formed after the material is folded, and the performance of the battery prepared by the material is poor. The spacing is too close, the technical difficulty is larger, the implementation is difficult, a large number of experiments show that when the rotating speed ratio of three groups of rollers is 1: 1.05-1.15: 1.15-1.25, the spacing of the first group of rollers is preferably 0.01-0.03 mm, the spacing of the second group of rollers is 0.010-0.20 mm, the spacing of the third group of rollers is 0.01-0.02 mm, the distribution of ethyl orthosilicate, sodium bicarbonate and ammonia water in the thermoplastic organic film is uniform, and the battery prepared from the material has good performance.
Further preferably, the small amount of magnesium powder in the step (2) is 0.03-0.08 g/cm2。
Further preferably, the high-temperature carbonization process in the step (3) is performed at a constant temperature of 200-210 ℃ for 30-36 min, the temperature is increased to 690-710 ℃, the temperature is kept for 1.9-2.2 h, and then the temperature is increased to 1000-1100 ℃ for carbonization for 5.0-5.5 h.
The high-temperature carbonization process in the step (3) is divided into three stages, carbonization is carried out slowly, the temperature is kept constant at 200-210 ℃ for 30-36 min, the temperature is increased to 690-710 ℃, the temperature is kept constant for 1.9-2.2 h, the temperature is increased to 1000-1100 ℃, carbonization is carried out for 5.0-5.5 h, the uniformity of the obtained film is good, pores formed by carbonization are small and few, and if carbonization is carried out directly at 1000-1100 ℃ for 5.0-5.5 h, the obtained material has many and large pores. A large number of experiments show that the high-temperature carbonization process has good effects when the temperature is kept constant at 200 ℃ for 30min, the temperature is kept constant at 700 ℃ for 2h and the temperature is kept constant at 1000 ℃ for 5h, so that the folded film is preferably kept constant at 200 ℃ for 30min, the temperature is kept constant at 700 ℃ for 2h and the temperature is kept constant at 1000 ℃ for 5h in the high-temperature carbonization process in the step (3).
Further preferably, the acid washing and water washing in the step (4) are to soak the sintered film for 30-60 min by using dilute hydrochloric acid, and to wash the film to be neutral by using deionized water.
Compared with the prior art, the invention has the outstanding characteristics and excellent effects that:
1. the invention soaks silicate ester into the inner hole of the film by a simple calendaring and stretching process, hydrolyzes the silicate ester into silicon oxide in an alkaline environment, and obtains the silicon-embedded carbon film by high-temperature magnesiothermic reduction and carbonization. The obtained film can be directly used as a lithium ion battery cathode material, and the preparation method and the process are extremely simple and are suitable for large-scale industrial production.
2. The silicon-embedded carbon film prepared by the method has good cycle performance, and the capacity, the first cycle efficiency and the cycle times are all superior to those of the existing commercial silicon-carbon cathode.
Drawings
FIG. 1 is a schematic view of a process flow
Wherein 1 is a thermoplastic organic film, 2 is a spray head ⑴, 3 is tetraethoxysilane, 4 is a roller ⑴, 5 is a spray head ⑵, 6 is a supersaturated aqueous solution of sodium bicarbonate, 7 is a roller ⑵, 8 is a spray head ⑶, 9 is ammonia water, and 10 is a roller ⑶.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1
Preparing a silicon-carbon composite film:
(1) using a thermoplastic organic matter film polyimide film as a raw material, placing the film in rolling equipment with three groups of rollers for stretching, wherein the rotating speed ratio of the three groups of rollers is 1:1.1: 1.2; rolling at 300 ℃, as shown in figure 1, spraying ethyl orthosilicate in front of a first group of rollers, spraying supersaturated sodium bicarbonate aqueous solution between the first group of rollers and a second group of rollers, and spraying 3mol/L ammonia water between the second group of rollers and a third group of rollers; the distance between the first group of rollers is 0.02mm, the distance between the second group of rollers is 0.015mm, and the distance between the third group of rollers is 0.01 mm;
(2) drying the thermoplastic organic film stretched in the step (1), and uniformly spraying a small amount of 0.05g/cm on the surface of the thermoplastic organic film2Magnesium powder is folded and cut to form a thermoplastic organic film with 4 layers;
(3) high-temperature carbonization: heating the thermoplastic organic film folded and cut in the step (2) to 200 ℃ under the protection of Ar gas, keeping the temperature for 30min, then heating to 700 ℃ and keeping the temperature for 2h, and heating to 1000 ℃ for carbonization for 5 h;
(4) and (4) soaking the thermoplastic organic film carbonized at the high temperature in the step (3) for 30min by using dilute hydrochloric acid, washing the film to be neutral by using deionized water, and drying the film to obtain the required composite film.
The obtained silicon-embedded carbon film is cut into a wafer with phi of 1 cm. And (3) bonding the copper foil, assembling the button cell with lithium iron phosphate and EC/PC electrolyte, testing the first charge-discharge efficiency and gram capacity of the cell at the current of 0.1C, and testing the cycle performance of the cell at the current of 1C. The results of the tests are detailed in table 1.
Example 2
Preparing a silicon-carbon composite film:
(2) using a thermoplastic organic matter film polyimide film as a raw material, placing the film in rolling equipment with three groups of rollers for stretching, wherein the rotating speed ratio of the three groups of rollers is 1:1.05: 1.2; rolling at 300 ℃, as shown in figure 1, spraying ethyl orthosilicate before the first group of rollers, spraying supersaturated sodium bicarbonate aqueous solution between the first group of rollers and the second group of rollers, and spraying 4mol/L ammonia water between the second group of rollers and the third group of rollers; the distance between the first group of rollers is 0.02mm, the distance between the second group of rollers is 0.015mm, and the distance between the third group of rollers is 0.01 mm;
(2) drying the thermoplastic organic film stretched in the step (1), and uniformly spraying a small amount of 0.06g/cm on the surface of the thermoplastic organic film2Magnesium powder is folded and cut to form a thermoplastic organic film with 3 layers;
(3) high-temperature carbonization: heating the thermoplastic organic film folded and cut in the step (2) to 200 ℃ under the protection of Ar gas, keeping the temperature for 30min, then heating to 700 ℃ and keeping the temperature for 2h, and heating to 1000 ℃ for carbonization for 5 h;
(4) and (4) soaking the thermoplastic organic film carbonized at the high temperature in the step (3) for 30min by using dilute hydrochloric acid, washing the film to be neutral by using deionized water, and drying the film to obtain the required composite film.
The obtained silicon-embedded carbon film is cut into a wafer with phi of 1 cm. And (3) bonding the copper foil, assembling the button cell with lithium iron phosphate and EC/PC electrolyte, testing the first charge-discharge efficiency and gram capacity of the cell at the current of 0.1C, and testing the cycle performance of the cell at the current of 1C. The results of the tests are detailed in table 1.
Example 3
Preparing a silicon-carbon composite film:
(3) using a thermoplastic organic matter film polyimide film as a raw material, placing the film in rolling equipment with three groups of rollers for stretching, wherein the rotating speed ratio of the three groups of rollers is 1:1.1: 1.15; rolling at 300 ℃, as shown in figure 1, spraying ethyl orthosilicate in front of a first group of rollers, spraying supersaturated sodium bicarbonate aqueous solution between the first group of rollers and a second group of rollers, and spraying 5mol/L ammonia water between the second group of rollers and a third group of rollers; the distance between the first group of rollers is 0.02mm, the distance between the second group of rollers is 0.015mm, and the distance between the third group of rollers is 0.01 mm;
(2) drying the thermoplastic organic film stretched in the step (1), and uniformly spraying a small amount of 0.07g/cm on the surface of the thermoplastic organic film2Magnesium powder is folded and cut to form a thermoplastic organic film with 4 layers;
(3) high-temperature carbonization: heating the thermoplastic organic film folded and cut in the step (2) to 205 ℃ in Ar gas protective atmosphere, keeping the temperature for 30min, then heating to 700 ℃ and keeping the temperature for 2h, and heating to 1000 ℃ for carbonization for 5 h;
(4) and (4) soaking the thermoplastic organic film carbonized at the high temperature in the step (3) for 30min by using dilute hydrochloric acid, washing the film to be neutral by using deionized water, and drying the film to obtain the required composite film.
The obtained silicon-embedded carbon film is cut into a wafer with phi of 1 cm. And (3) bonding the copper foil, assembling the button cell with lithium iron phosphate and EC/PC electrolyte, testing the first charge-discharge efficiency and gram capacity of the cell at the current of 0.1C, and testing the cycle performance of the cell at the current of 1C. The results of the tests are detailed in table 1.
Example 4
Preparing a silicon-carbon composite film:
(4) using a thermoplastic organic matter film polyimide film as a raw material, placing the film in rolling equipment with three groups of rollers for stretching, wherein the rotating speed ratio of the three groups of rollers is 1:1.05: 1.15; rolling at 300 ℃, as shown in figure 1, spraying ethyl orthosilicate before the first group of rollers, spraying supersaturated sodium bicarbonate aqueous solution between the first group of rollers and the second group of rollers, and spraying 4mol/L ammonia water between the second group of rollers and the third group of rollers; the distance between the first group of rollers is 0.02mm, the distance between the second group of rollers is 0.015mm, and the distance between the third group of rollers is 0.01 mm;
(2) drying the thermoplastic organic film stretched in the step (1), and uniformly spraying a small amount of 0.06g/cm on the surface of the thermoplastic organic film2Magnesium powder is folded and cut to form a thermoplastic organic film with 3 layers;
(3) high-temperature carbonization: heating the thermoplastic organic film folded and cut in the step (2) to 200 ℃ under the protection of Ar gas, keeping the temperature for 30min, then heating to 700 ℃ and keeping the temperature for 2h, and heating to 1000 ℃ for carbonization for 5 h;
(4) soaking the thermoplastic organic film carbonized at the high temperature in the step (3) for 40min by using dilute hydrochloric acid, washing the film to be neutral by using deionized water, and drying the film to obtain the required composite film.
The obtained silicon-embedded carbon film is cut into a wafer with phi of 1 cm. And (3) bonding the copper foil, assembling the button cell with lithium iron phosphate and EC/PC electrolyte, testing the first charge-discharge efficiency and gram capacity of the cell at the current of 0.1C, and testing the cycle performance of the cell at the current of 1C. The results of the tests are detailed in table 1.
Example 5
Preparing a silicon-carbon composite film:
(5) using a thermoplastic organic matter film polyimide film as a raw material, placing the film in rolling equipment with three groups of rollers for stretching, wherein the rotating speed ratio of the three groups of rollers is 1:1.15: 1.2; rolling at 300 ℃, as shown in figure 1, spraying ethyl orthosilicate before the first group of rollers, spraying supersaturated sodium bicarbonate aqueous solution between the first group of rollers and the second group of rollers, and spraying 4mol/L ammonia water between the second group of rollers and the third group of rollers; the distance between the first group of rollers is 0.02mm, the distance between the second group of rollers is 0.015mm, and the distance between the third group of rollers is 0.01 mm;
(2) drying the thermoplastic organic film stretched in the step (1), and uniformly spraying a small amount of 0.06g/cm on the surface of the thermoplastic organic film2Magnesium powder is folded and cut to form a thermoplastic organic film with 4 layers;
(3) high-temperature carbonization: heating the thermoplastic organic film folded and cut in the step (2) to 200 ℃ under the protection of Ar gas, keeping the temperature for 30min, then heating to 710 ℃, keeping the temperature for 2h, heating to 1000 ℃, and carbonizing for 5 h;
(4) and (4) soaking the thermoplastic organic film carbonized at the high temperature in the step (3) for 30min by using dilute hydrochloric acid, washing the film to be neutral by using deionized water, and drying the film to obtain the required composite film.
The obtained silicon-embedded carbon film is cut into a wafer with phi of 1 cm. And (3) bonding the copper foil, assembling the button cell with lithium iron phosphate and EC/PC electrolyte, testing the first charge-discharge efficiency and gram capacity of the cell at the current of 0.1C, and testing the cycle performance of the cell at the current of 1C. The results of the tests are detailed in table 1.
Example 6
Preparing a silicon-carbon composite film:
(6) using a thermoplastic organic matter film polyimide film as a raw material, placing the film in rolling equipment with three groups of rollers for stretching, wherein the rotating speed ratio of the three groups of rollers is 1:1.05: 1.25; rolling at 300 ℃, as shown in figure 1, spraying ethyl orthosilicate before the first group of rollers, spraying supersaturated sodium bicarbonate aqueous solution between the first group of rollers and the second group of rollers, and spraying 4mol/L ammonia water between the second group of rollers and the third group of rollers; the distance between the first group of rollers is 0.02mm, the distance between the second group of rollers is 0.015mm, and the distance between the third group of rollers is 0.01 mm;
(2) drying the thermoplastic organic film stretched in the step (1), and uniformly spraying a small amount of 0.06g/cm on the surface of the thermoplastic organic film2Magnesium powder is folded and cut to form a thermoplastic organic film with 4 layers;
(3) high-temperature carbonization: heating the thermoplastic organic film folded and cut in the step (2) to 200 ℃ under the protection of Ar gas, keeping the temperature for 30min, then heating to 700 ℃ and keeping the temperature for 2h, and heating to 1050 ℃ for carbonization for 5 h;
(4) and (4) soaking the thermoplastic organic film carbonized at the high temperature in the step (3) for 30min by using dilute hydrochloric acid, washing the film to be neutral by using deionized water, and drying the film to obtain the required composite film.
The obtained silicon-embedded carbon film is cut into a wafer with phi of 1 cm. And (3) bonding the copper foil, assembling the button cell with lithium iron phosphate and EC/PC electrolyte, testing the first charge-discharge efficiency and gram capacity of the cell at the current of 0.1C, and testing the cycle performance of the cell at the current of 1C. The results of the tests are detailed in table 1.
Comparative example 1
The method comprises the steps of adding polyvinylpyrrolidone with the mass of 1.5% of silicon carbon powder into silicon carbon composite powder purchased from Shaanxi six-membered carbon crystal Limited company, pressing the silicon carbon composite powder into a sheet serving as a negative electrode, bonding the sheet with copper foil, assembling the sheet with lithium iron phosphate and EC/PC electrolyte to form a button cell, testing the first charge-discharge efficiency and gram capacity of the cell at the current of 0.1C, and testing the cycle performance of the cell at the current of 1C. The results of the tests are detailed in table 1.
Table 1:
| gram volume mah/g | First effect | Number of cycles (80% residual capacity) | |
| Example 1 | 483 | 83% | 86 |
| Example 2 | 482 | 82% | 83 |
| Example 3 | 479 | 86% | 75 |
| Example 4 | 481 | 84% | 85 |
| Example 5 | 480 | 83% | 79 |
| Example 6 | 478 | 89% | 74 |
| Comparative example 1 | 447 | 81% | 34 |
According to the tests, the capacity, the first cycle efficiency and the cycle times of the silicon-embedded carbon film prepared by the embodiment of the invention are superior to those of the existing commercial silicon-carbon cathode.
Claims (10)
1. A preparation method of a lithium battery silicon-carbon composite film negative electrode is characterized by comprising the following steps: the method comprises the following steps:
(1) the method comprises the following steps of using a thermoplastic organic film as a raw material, placing the film in rolling equipment for stretching, and spraying ethyl orthosilicate, sodium bicarbonate and ammonia water on rollers, wherein the thermoplastic organic film sequentially passes through three groups of rollers, and the rotating speed ratio of the three groups of rollers is 1: 1.05-1.15: 1.15-1.25;
(2) drying the stretched thermoplastic organic film obtained in the step (1), uniformly spraying a small amount of magnesium powder on the surface of the film, folding and cutting, wherein the number of folded thermoplastic organic films is 3-5;
(3) carrying out high-temperature carbonization on the thermoplastic organic film folded and cut in the step (2), wherein the high-temperature carbonization process comprises the steps of keeping the temperature at 195-210 ℃ for 28-36 min, heating to 690-720 ℃ for 1.9-2.5 h, then heating to 995-1100 ℃ for carbonization for 4.8-5.5 h, and using Ar gas as protective atmosphere;
(4) and (4) carrying out acid washing, water washing and drying on the thermoplastic organic film carbonized at the high temperature in the step (3) to obtain the required composite film.
2. The method for preparing the silicon-carbon composite film negative electrode of the lithium battery as claimed in claim 1, wherein the method comprises the following steps: the thermoplastic organic film in the step (1) is made of one of polyimide or polyacrylic acid.
3. The method for preparing the silicon-carbon composite film negative electrode of the lithium battery as claimed in claim 1, wherein the method comprises the following steps: the sodium bicarbonate in the step (1) is a supersaturated sodium bicarbonate water solution, and the concentration of ammonia water is 2-5 mol/L.
4. The method for preparing the silicon-carbon composite film negative electrode of the lithium battery as claimed in claim 1, wherein the method comprises the following steps: the rotating speed ratio of the three groups of rollers in the step (1) is 1:1.1: 1.2.
5. The method for preparing the silicon-carbon composite film negative electrode of the lithium battery as claimed in claim 1, wherein the method comprises the following steps: in the rolling process in the step (1), the rolling temperature is the softening temperature of the organic film.
6. The method for preparing the silicon-carbon composite film negative electrode of the lithium battery as claimed in claim 1, wherein the method comprises the following steps: the hot three groups of rollers in the step (1) are respectively a first group of rollers, a second group of rollers and a third group of rollers, wherein ethyl orthosilicate is sprayed in front of the first group of rollers, a sodium bicarbonate water solution is sprayed between the first group of rollers and the second group of rollers, and ammonia water is sprayed between the second group of rollers and the third group of rollers; the distance between the first group of rollers is preferably 0.01-0.03 mm, the distance between the second group of rollers is 0.010-0.20 mm, and the distance between the third group of rollers is 0.01-0.02 mm.
7. The method for preparing the silicon-carbon composite film negative electrode of the lithium battery as claimed in claim 1, wherein the method comprises the following steps: the small amount of magnesium powder in the step (2) is 0.03-0.08 g/cm2。
8. The method for preparing the silicon-carbon composite film negative electrode of the lithium battery as claimed in claim 1, wherein the method comprises the following steps: the high-temperature carbonization process in the step (3) is carried out for 30-36 min at the constant temperature of 200-210 ℃, the temperature is increased to 690-710 ℃, the constant temperature is kept for 1.9-2.2 h, and then the temperature is increased to 1000-1100 ℃ for carbonization for 5.0-5.5 h.
9. The method for preparing the silicon-carbon composite film negative electrode of the lithium battery as claimed in claim 1, wherein the method comprises the following steps: in the high-temperature carbonization process in the step (3), the folded film is subjected to constant temperature of 200 ℃ for 30min, 700 ℃ for 2h and 1000 ℃ for carbonization for 5 h.
10. The method for preparing the silicon-carbon composite film negative electrode of the lithium battery as claimed in claim 1, wherein the method comprises the following steps: and (4) pickling and washing, namely soaking the sintered film for 30-60 min by using dilute hydrochloric acid, and washing the film to be neutral by using deionized water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911130722.8A CN110867562B (en) | 2019-11-19 | 2019-11-19 | Preparation method of lithium battery silicon-carbon composite film cathode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911130722.8A CN110867562B (en) | 2019-11-19 | 2019-11-19 | Preparation method of lithium battery silicon-carbon composite film cathode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110867562A true CN110867562A (en) | 2020-03-06 |
| CN110867562B CN110867562B (en) | 2020-12-22 |
Family
ID=69655297
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911130722.8A Active CN110867562B (en) | 2019-11-19 | 2019-11-19 | Preparation method of lithium battery silicon-carbon composite film cathode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110867562B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111785969A (en) * | 2020-07-08 | 2020-10-16 | 吴耀帮 | Preparation method of porous nano Si-SiO2-C @ graphite composite lithium ion battery cathode powder and lithium ion battery |
| CN112038567A (en) * | 2020-08-12 | 2020-12-04 | 北京化工大学 | Continuous production device and production process of electrode |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20130124813A (en) * | 2012-05-07 | 2013-11-15 | 강윤규 | Powder composite of silicon and carbon for the use of anode material in secondary battery |
| CN106410155A (en) * | 2016-10-28 | 2017-02-15 | 林天安 | Preparing method of graphene silica carbon negative material |
| CN107359306A (en) * | 2017-05-23 | 2017-11-17 | 中国第汽车股份有限公司 | A kind of preparation method of the compound silicon-carbon cathode material of organic carbon |
| CN109980194A (en) * | 2019-02-27 | 2019-07-05 | 福建翔丰华新能源材料有限公司 | A kind of preparation method of lithium ion battery silicon-carbon cathode material |
| CN110197900A (en) * | 2019-06-20 | 2019-09-03 | 厦门大学 | A kind of Si-C composite material and its preparation method and application |
-
2019
- 2019-11-19 CN CN201911130722.8A patent/CN110867562B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20130124813A (en) * | 2012-05-07 | 2013-11-15 | 강윤규 | Powder composite of silicon and carbon for the use of anode material in secondary battery |
| CN106410155A (en) * | 2016-10-28 | 2017-02-15 | 林天安 | Preparing method of graphene silica carbon negative material |
| CN107359306A (en) * | 2017-05-23 | 2017-11-17 | 中国第汽车股份有限公司 | A kind of preparation method of the compound silicon-carbon cathode material of organic carbon |
| CN109980194A (en) * | 2019-02-27 | 2019-07-05 | 福建翔丰华新能源材料有限公司 | A kind of preparation method of lithium ion battery silicon-carbon cathode material |
| CN110197900A (en) * | 2019-06-20 | 2019-09-03 | 厦门大学 | A kind of Si-C composite material and its preparation method and application |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111785969A (en) * | 2020-07-08 | 2020-10-16 | 吴耀帮 | Preparation method of porous nano Si-SiO2-C @ graphite composite lithium ion battery cathode powder and lithium ion battery |
| CN112038567A (en) * | 2020-08-12 | 2020-12-04 | 北京化工大学 | Continuous production device and production process of electrode |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110867562B (en) | 2020-12-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112582615B (en) | One-dimensional porous silicon-carbon composite negative electrode material, preparation method and application thereof | |
| CN102208634B (en) | Porous silicon/carbon composite material and preparation method thereof | |
| CN103022436B (en) | Electrode composite material preparation method | |
| CN103779544B (en) | A kind of preparation method of porous silicon/carbon composite material | |
| CN114524425B (en) | Hard carbon material, preparation method thereof and application thereof in sodium ion battery | |
| CN109599546A (en) | Asphalt carbon-coated natural mixed graphite material and method for preparing lithium ion battery cathode by using same | |
| CN105390672A (en) | Preparation method for three-dimensional nitrogen-doped mesoporous carbon ultra-thin nanosheet material | |
| CN108269982B (en) | Composite material, preparation method thereof and application thereof in lithium ion battery | |
| CN105489866B (en) | A kind of lithium ion battery and its anode material and preparation method | |
| CN108258211B (en) | Method for preparing titanium dioxide/graphene composite material by supercritical carbon dioxide fluid and application | |
| CN107565103B (en) | Porous silicon/graphene composite material and preparation method and application thereof | |
| CN103035881B (en) | Preparation method of graphene-silicon composite material | |
| CN111244414A (en) | Method for preparing silicon-carbon negative electrode material by magnesiothermic reduction | |
| CN104091952A (en) | Novel negative electrode material for lithium ion battery and preparation method of negative electrode material | |
| CN105845918A (en) | High capacity porous silicon material, preparation method and application thereof | |
| CN110867562B (en) | Preparation method of lithium battery silicon-carbon composite film cathode | |
| CN112875680B (en) | Preparation method of flaky Fe-based alloy catalytic growth carbon nanotube array | |
| CN110767891A (en) | Preparation method of porous spherical silicon-based composite anode material | |
| CN104393275A (en) | Preparation method of carbon-coated lithium titanate battery material | |
| CN113998700B (en) | Method for preparing Si/SiC@C anode material by taking micro silicon powder as raw material | |
| CN110534710A (en) | Silicon/carbon composite and its preparation method and application | |
| CN114388738A (en) | Silicon-based negative electrode material and preparation method and application thereof | |
| CN105870434B (en) | Method for doping silicon powder | |
| CN112186151A (en) | Cobalt phosphide nanoparticle inlaid carbon nanosheet array material and preparation and application thereof | |
| CN113488376B (en) | Two-dimensional silicon dioxide and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20211115 Address after: Room 419, building a, management committee of Dongying Economic and Technological Development Zone, No. 59, Fuqian street, Dongying District, Dongying City, Shandong Province, 257100 Patentee after: Dongying dongkai New Material Industrial Park Co.,Ltd. Address before: 610091 block 4, Donghai Road, Jiaolong industrial port, Qingyang District, Chengdu, Sichuan Patentee before: CHENDU NEW KELI CHEMICAL SCIENCE Co.,Ltd. CHINA |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20221227 Address after: 257091 Room 101, Building 5, Science and Technology Enterprise Accelerator, No. 17, Xinghuahe Road, Dongying Development Zone, Shandong Province Patentee after: Dongying Dongkai New Material Technology Research and Development Co.,Ltd. Address before: Room 419, building a, management committee of Dongying Economic and Technological Development Zone, No. 59, Fuqian street, Dongying District, Dongying City, Shandong Province, 257100 Patentee before: Dongying dongkai New Material Industrial Park Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240126 Address after: Room 405, Building A, Technology Enterprise Accelerator, No. 17 Xinghuahe Road, Development Zone, Dongying City, Shandong Province, 257091 Patentee after: Dongying Dongkai Industrial Park Operation Management Co.,Ltd. Country or region after: China Address before: 257091 Room 101, Building 5, Science and Technology Enterprise Accelerator, No. 17, Xinghuahe Road, Dongying Development Zone, Shandong Province Patentee before: Dongying Dongkai New Material Technology Research and Development Co.,Ltd. Country or region before: China |