CN117525321A - Preparation method of lithium ion battery negative electrode silicon-carbon composite material - Google Patents
Preparation method of lithium ion battery negative electrode silicon-carbon composite material Download PDFInfo
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- CN117525321A CN117525321A CN202311476818.6A CN202311476818A CN117525321A CN 117525321 A CN117525321 A CN 117525321A CN 202311476818 A CN202311476818 A CN 202311476818A CN 117525321 A CN117525321 A CN 117525321A
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- 239000002153 silicon-carbon composite material Substances 0.000 title claims abstract description 91
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title claims abstract description 78
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 102
- 239000000463 material Substances 0.000 claims abstract description 66
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 35
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 24
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 24
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 20
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 20
- 229960000789 guanidine hydrochloride Drugs 0.000 claims abstract description 17
- PJJJBBJSCAKJQF-UHFFFAOYSA-N guanidinium chloride Chemical compound [Cl-].NC(N)=[NH2+] PJJJBBJSCAKJQF-UHFFFAOYSA-N 0.000 claims abstract description 17
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000243 solution Substances 0.000 claims description 113
- 238000006243 chemical reaction Methods 0.000 claims description 77
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 66
- 238000000034 method Methods 0.000 claims description 59
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 58
- 239000011248 coating agent Substances 0.000 claims description 54
- 238000000576 coating method Methods 0.000 claims description 54
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 44
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 33
- 150000001875 compounds Chemical class 0.000 claims description 33
- 239000006228 supernatant Substances 0.000 claims description 33
- 238000000151 deposition Methods 0.000 claims description 32
- 230000008021 deposition Effects 0.000 claims description 32
- 238000004070 electrodeposition Methods 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 24
- 239000011259 mixed solution Substances 0.000 claims description 23
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 22
- 239000002244 precipitate Substances 0.000 claims description 22
- 239000001632 sodium acetate Substances 0.000 claims description 22
- 235000017281 sodium acetate Nutrition 0.000 claims description 22
- 239000012528 membrane Substances 0.000 claims description 20
- 239000001509 sodium citrate Substances 0.000 claims description 20
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 18
- 239000012224 working solution Substances 0.000 claims description 18
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- 238000000502 dialysis Methods 0.000 claims description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 11
- -1 polytetrafluoroethylene Polymers 0.000 claims description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 11
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 11
- 239000012498 ultrapure water Substances 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 229910052697 platinum Inorganic materials 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000012465 retentate Substances 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052744 lithium Inorganic materials 0.000 abstract description 9
- 238000013508 migration Methods 0.000 abstract description 6
- 230000005012 migration Effects 0.000 abstract description 6
- 239000003638 chemical reducing agent Substances 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 239000010406 cathode material Substances 0.000 abstract description 4
- 239000006087 Silane Coupling Agent Substances 0.000 abstract description 3
- 238000009825 accumulation Methods 0.000 abstract description 3
- 238000013461 design Methods 0.000 abstract description 3
- YPSNMKHPDJVGEX-UHFFFAOYSA-L potassium;sodium;3-carboxy-3-hydroxypentanedioate Chemical compound [Na+].[K+].OC(=O)CC(O)(C([O-])=O)CC([O-])=O YPSNMKHPDJVGEX-UHFFFAOYSA-L 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 230000014759 maintenance of location Effects 0.000 description 18
- 238000002604 ultrasonography Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 239000003575 carbonaceous material Substances 0.000 description 8
- 230000010355 oscillation Effects 0.000 description 8
- 238000005119 centrifugation Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 238000009210 therapy by ultrasound Methods 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000010405 anode material Substances 0.000 description 4
- 239000005543 nano-size silicon particle Substances 0.000 description 4
- 239000002210 silicon-based material Substances 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000017525 heat dissipation Effects 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011856 silicon-based particle Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000012217 deletion Methods 0.000 description 1
- 230000037430 deletion Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of a lithium ion battery cathode silicon-carbon composite material, and belongs to the technical field of battery materials. Creatively designs a silicon-carbon composite material based on (3-aminopropyl) trimethoxysilane, guanidine hydrochloride and modified carbon nano tube as main bodies, and assists a plurality of comprehensively obtained composite materials such as hexadecylamine, sodium citrate potassium reducer and the like, and the materials are synergistic mutually to promote the recyclable capacity of the lithium battery; meanwhile, the silane coupling agent and the conductive carbon nano tube are combined for the first time, so that effective conductive cycle times are achieved; in addition, ferric chloride and the like play a role in protecting the lithium battery and maintain the overall efficiency of the lithium battery. The silicon-carbon composite material is beneficial to effective migration of lithium ions, avoids concentration of lithium ions and stress accumulation, causes less migration quantity of effective lithium ions, and further has low actual capacity, and hexadecylamine can meet the safety of a cathode material, and particularly, the hexadecylamine is wrapped on the surface of graphene.
Description
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to a preparation method of a silicon-carbon composite material for a lithium ion battery cathode.
Background
The silicon-carbon composite material of the lithium ion battery cathode is an important cathode material for improving the energy density and the cycle life of the lithium ion battery. The following is related to the silicon-carbon composite material of the lithium ion battery cathode:
1. application of silicon material: silicon has a higher theoretical capacity (4200 mAh/g) than conventional negative electrode materials (e.g., graphite), and thus has been widely studied as a candidate for negative electrode materials for lithium ion batteries. However, the silicon material has a large capacity expansion during lithium ion intercalation/deintercalation, resulting in volume change and structural destruction of the material, causing problems of capacity degradation and short cycle life of the battery.
2. Silicon-carbon composite material: to overcome the capacity fade and cycle life problems of silicon materials, silicon may be composited with carbon materials. The silicon-carbon composite material can realize the fixation and restraint of the silicon nano particles by embedding the silicon nano particles into the carbon-based anode material, thereby reducing the volume expansion of the silicon particles, improving the structural stability of the material and prolonging the cycle life of the battery.
3. The preparation method of the silicon-carbon composite material comprises the following steps: the preparation method of the silicon-carbon composite material is various, and common methods include a mechanical mixing method, a solution method, a heat treatment method, an electrochemical deposition method and the like. The methods can realize the uniform dispersion and combination of the silicon nano particles and the carbon-based material to form a silicon-carbon composite structure.
4. Selection and modification of carbon materials: the carbon material plays a role in stabilizing silicon nano particles and conducting electricity in the silicon-carbon composite material. Common carbon materials include natural graphite, carbon black, carbon nanotubes, graphene, and the like. By selecting proper carbon materials and carrying out surface modification, the conductivity, the mechanical strength and the structural stability of the material can be enhanced, and the electrochemical performance of the silicon-carbon composite material can be improved.
5. Additives and coating materials: additives and cladding materials may be incorporated to further enhance the properties of the silicon carbon composite. Additives such as polymer micelles, conductive additives, binders, and the like can improve the conductivity, structural stability, and adhesive strength of the material. The coating material such as silicon dioxide, silicon nitride, aluminum oxide and the like can form a protective layer to prevent the electrolyte in the electrolyte from directly contacting with silicon, reduce the volume change and electrochemical reaction of silicon particles and improve the cycle life of the battery.
In summary, the research of the silicon-carbon composite material of the lithium ion battery cathode is not separated from the background technologies such as application of the silicon material, preparation method of the silicon-carbon composite material, selection and modification of the carbon material, application of the additive and the coating material, and the like. The continuous development and innovation of the technologies provides a foundation and a solution for improving the energy density, the cycle life and the safety of the lithium ion battery. By optimizing the structure and the performance of the silicon-carbon composite material, the high energy density, the long cycle life and the good safety performance of the lithium ion battery can be realized, and the lithium ion battery is promoted to be widely applied to the fields of electric vehicles, portable equipment, energy storage systems and the like.
The Chinese patent application publication No. CN116613299A discloses a preparation method of a novel silicon-carbon anode material and a product thereof, and the technical scheme is as follows: the preparation method of the novel silicon-carbon anode material comprises the following steps:
(1) Under inert atmosphere, placing a porous carbon material serving as a substrate into a deposition furnace, and heating to 400-700 ℃;
(2) Introducing a mixed gas A containing a silicon source gas and a carbon source gas into a deposition furnace, adjusting a tail gas pipe air pressure valve to ensure that the pressure in the furnace is always kept at 5-10 MPa in the deposition process, and continuously introducing gas to perform vapor deposition to obtain an intermediate product;
(3) And cooling to 200-300 ℃, and introducing the mixed gas B containing the oxygen-containing gas and the carrier gas into a deposition furnace, and performing surface passivation and post-treatment to obtain the novel silicon-carbon anode material. Although the effect is better, the process requires higher temperature and higher pressure, the production cost is high, and the environmental pollution is large.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a preparation method of a lithium ion battery anode silicon-carbon composite material, which can effectively maintain the circulation capacity of a battery through testing.
In order to achieve the above purpose, the present invention provides the following technical solutions:
a preparation method of a silicon-carbon composite material of a lithium ion battery cathode,
the method comprises the following steps:
guanidine hydrochloride, (3-aminopropyl) trimethoxysilane and ultrapure water are mixed according to the mass volume ratio (6 mg-20 mg): (0.2 mL-3 mL): (1 mL-5 mL) and mixing and dissolving, and fully oscillating by a vortex machine to obtain a mixed solution; transferring the mixed solution into a hydrothermal synthesis reaction kettle with a polytetrafluoroethylene lining for reaction, heating to 140-180 ℃ by using an oven for reaction, controlling the reaction time to 6 hours to obtain a reaction solution, and cooling the reaction solution to room temperature after the reaction is finished; centrifuging the reaction solution, and collecting supernatant;
next, the collected supernatant was mixed with sodium acetate, hexadecylamine and sodium citrate, wherein the mass-to-volume ratio between the supernatant, sodium acetate, hexadecylamine and sodium citrate was (10 mL-15 mL): (0.5 g-3 g): (0.1 mL-1 mL): (0.1 g-0.6 g), mixing at 200rpm for 2h at room temperature, dialyzing the solution with 3000Da dialysis membrane, recovering the retentate, and dispersing in 30mL of N, N-dimethylformamide solution to obtain viscous compound;
finally, the obtained sticky compound is evenly mixed with the modified carbon nano tube, the propylene glycol, the ferric chloride and the acetone by ultrasonic, wherein the mass volume ratio of the sticky compound to the modified carbon nano tube to the propylene glycol to the ferric chloride to the acetone is (2 g-10 g): 0.1g:6mL:0.2g:10mL, collecting a tan precipitate, re-suspending the tan precipitate in ethanol solution with five times mass to obtain a coating material, and carrying out deposition treatment on graphene and the coating material, wherein the mass-volume ratio between the graphene and the coating material is (10 g-30 g): (10 mL-30 mL), and then placing for 12h at 80 ℃ under vacuum condition to obtain the lithium ion battery anode silicon-carbon composite material.
The preparation method of the lithium ion battery cathode silicon-carbon composite material,
the preparation method of the modified carbon nano tube comprises the following steps:
dispersing 0.1g of p-phenylenediamine and 50mg of carbon nano tube into 10mL of ammonia water with mass fraction of 10%, stirring and refluxing for 8h at 90 ℃, filtering by using a 0.22um microporous filter membrane, and finally drying in vacuum at 60 ℃ for 60min to obtain the modified carbon nano tube.
The preparation method of the lithium ion battery cathode silicon-carbon composite material,
the deposition treatment method is an electrochemical deposition method.
The preparation method of the lithium ion battery cathode silicon-carbon composite material,
the electrochemical deposition method is as follows:
and (3) taking ethanol solution containing a coating material as a working solution, graphene as a working electrode, and a platinum electrode as a counter electrode, and carrying out deposition treatment.
The preparation method of the lithium ion battery cathode silicon-carbon composite material,
wherein the mass volume ratio of the coating material in the working solution to the ethanol solution is 10g:200mL.
The preparation method of the lithium ion battery cathode silicon-carbon composite material,
the parameters of the electrochemical deposition method are as follows:
the time was 200min and the voltage was 5V.
Compared with the prior art, the invention has the beneficial effects that:
the invention innovatively designs a silicon-carbon composite material based on (3-aminopropyl) trimethoxysilane, guanidine hydrochloride and modified carbon nano tube as main bodies, and assists a composite material obtained by synthesizing various substances such as hexadecylamine, sodium citrate potassium serving as a reducing agent and the like, wherein the substances are synergistic mutually, and play a role in promoting the recyclable capacity of a lithium battery; meanwhile, the silane coupling agent and the conductive carbon nano tube are combined for the first time, so that effective conductive cycle times are achieved; in addition, it is supposed that ferric chloride and the like play a role in protecting the lithium battery, bring a certain heat dissipation effect and maintain the overall efficiency of the lithium battery. The silicon-carbon composite material is beneficial to effective migration of lithium ions, avoids concentration of lithium ions and stress accumulation, causes less migration quantity of effective lithium ions, and further has low actual capacity, and hexadecylamine can meet the safety of a cathode material by wrapping the surface of graphene.
Detailed Description
The following describes the technical solutions in the embodiments of the present invention in detail, and the described embodiments are only some of the embodiments of the present invention. All other embodiments, which are derived by a person skilled in the art based on the embodiments of the invention, fall within the scope of protection of the invention. The invention is further described below in connection with specific embodiments.
Preparation example
Example 1
A preparation method of a silicon-carbon composite material of a lithium ion battery cathode,
the method comprises the following steps:
guanidine hydrochloride, (3-aminopropyl) trimethoxysilane and ultrapure water are mixed according to the mass volume ratio of 12mg:1mL:2mL is mixed and dissolved, and a vortex machine is adopted for full oscillation to obtain a mixed solution; transferring the mixed solution into a hydrothermal synthesis reaction kettle with a polytetrafluoroethylene lining for reaction, heating to 160 ℃ by using an oven for reaction, controlling the reaction time to 6 hours to obtain a reaction solution, and cooling the reaction solution to room temperature after the reaction is finished; centrifuging the reaction solution at 10000rpm and 4deg.C for 30min, and collecting supernatant;
next, the collected supernatant was mixed with sodium acetate, hexadecylamine and sodium citrate, wherein the mass-to-volume ratio between the supernatant, sodium acetate, hexadecylamine and sodium citrate was 12mL:1g:0.5mL:0.2g, mixing uniformly at 200rpm for 2 hours at room temperature by a shaker until the solution is green, dialyzing the solution by using a dialysis membrane of 3000Da, recovering a retention solution, and dispersing the retention solution in 30mL of N, N-dimethylformamide solution to obtain a viscous compound;
finally, carrying out ultrasonic mixing on the obtained sticky compound, the modified carbon nano tube, the propylene glycol, the ferric chloride and the acetone, wherein the mass volume ratio of the sticky compound to the modified carbon nano tube to the propylene glycol to the ferric chloride to the acetone is 5g:0.1g:6mL:0.2g:10mL, wherein the power of ultrasound is 300W, the time of ultrasound is 1h, after ultrasound treatment, centrifugation is carried out for 10min at 2000rpm and 4 ℃, the tan precipitate is collected, the tan precipitate is resuspended in ethanol solution with five times mass to obtain a coating material, and graphene and the coating material are subjected to deposition treatment, wherein the mass-volume ratio between the graphene and the coating material is 20g:20mL, then placed under vacuum at 80℃for 12 h.
The preparation method of the lithium ion battery cathode silicon-carbon composite material,
the preparation method of the modified carbon nano tube comprises the following steps:
dispersing 0.1g of p-phenylenediamine and 50mg of carbon nano tube into 10mL of ammonia water with mass fraction of 10%, stirring and refluxing for 8h at 90 ℃, filtering by using a 0.22um microporous filter membrane, and finally drying in vacuum at 60 ℃ for 60min to obtain the nano-crystalline p-phenylenediamine.
The preparation method of the lithium ion battery cathode silicon-carbon composite material,
the carbon nanotubes were purchased from Guangdong Weng Jiang chemical agent Co., ltd, with CAS number 308068-56-6.
The preparation method of the lithium ion battery cathode silicon-carbon composite material,
the deposition treatment method is an electrochemical deposition method.
The preparation method of the lithium ion battery cathode silicon-carbon composite material,
the electrochemical deposition method is as follows:
and (3) taking ethanol solution containing a coating material as a working solution, graphene as a working electrode, and a platinum electrode as a counter electrode, and carrying out deposition treatment.
The preparation method of the lithium ion battery cathode silicon-carbon composite material,
wherein the mass volume ratio of the coating material in the working solution to the ethanol solution is 10g:200mL.
The preparation method of the lithium ion battery cathode silicon-carbon composite material,
the parameters of the electrochemical deposition method are as follows:
the time was 200min and the voltage was 5V.
Example 2
Substantially the same as in example 1, the following differences were found:
a preparation method of a silicon-carbon composite material of a lithium ion battery cathode,
the method comprises the following steps:
guanidine hydrochloride, (3-aminopropyl) trimethoxysilane and ultrapure water are mixed according to the mass volume ratio of 6mg:3mL:1m, mixing and dissolving, and fully oscillating by adopting a vortex machine to obtain a mixed solution; transferring the mixed solution into a hydrothermal synthesis reaction kettle with a polytetrafluoroethylene lining for reaction, heating to 140 ℃ by using an oven for reaction, controlling the reaction time to 6 hours to obtain a reaction solution, and cooling the reaction solution to room temperature after the reaction is finished; centrifuging the reaction solution, and collecting supernatant;
next, the collected supernatant was mixed with sodium acetate, hexadecylamine and sodium citrate, wherein the mass-to-volume ratio between the supernatant, sodium acetate, hexadecylamine and sodium citrate was 10mL:3g:0.1mL:0.6g, mixing uniformly at 200rpm for 2 hours at room temperature by a shaker until the solution is green, dialyzing the solution by using a dialysis membrane of 3000Da, recovering a retention solution, and dispersing the retention solution in 30mL of N, N-dimethylformamide solution to obtain a viscous compound;
finally, carrying out ultrasonic mixing on the obtained sticky compound, the modified carbon nano tube, the propylene glycol, the ferric chloride and the acetone, wherein the mass volume ratio of the sticky compound to the modified carbon nano tube to the propylene glycol to the ferric chloride to the acetone is 2g:0.1g:6mL:0.2g:10mL, collecting a tan precipitate, re-suspending the tan precipitate in ethanol solution with five times of mass to obtain a coating material, and carrying out deposition treatment on graphene and the coating material, wherein the mass-volume ratio between the graphene and the coating material is 10g:30mL, and then placing for 12h under the vacuum condition at 80 ℃ to obtain the silicon-carbon composite material of the lithium ion battery cathode.
Example 3
Substantially the same as in example 1, the following differences were found:
a preparation method of a silicon-carbon composite material of a lithium ion battery cathode,
the method comprises the following steps:
guanidine hydrochloride, (3-aminopropyl) trimethoxysilane and ultrapure water are mixed according to the mass volume ratio of 20mg:0.2mL:5mL of the mixed solution is mixed and dissolved, and the vortex machine is adopted for full oscillation to obtain mixed solution; transferring the mixed solution into a hydrothermal synthesis reaction kettle with a polytetrafluoroethylene lining for reaction, heating to 180 ℃ by using an oven for reaction, controlling the reaction time to 6 hours to obtain a reaction solution, and cooling the reaction solution to room temperature after the reaction is finished; centrifuging the reaction solution, and collecting supernatant;
next, the collected supernatant was mixed with sodium acetate, hexadecylamine and sodium citrate, wherein the mass-to-volume ratio between the supernatant, sodium acetate, hexadecylamine and sodium citrate was 15mL:0.5g:1mL:0.1g, mixing uniformly at 200rpm for 2 hours at room temperature by a shaker until the solution is green, dialyzing the solution by using a dialysis membrane of 3000Da, recovering a retention solution, and dispersing the retention solution in 30mL of N, N-dimethylformamide solution to obtain a viscous compound;
finally, carrying out ultrasonic mixing on the obtained sticky compound, the modified carbon nano tube, the propylene glycol, the ferric chloride and the acetone, wherein the mass volume ratio of the sticky compound to the modified carbon nano tube to the propylene glycol to the ferric chloride to the acetone is 10g:0.1g:6mL:0.2g:10mL, collecting a tan precipitate, re-suspending the tan precipitate in ethanol solution with five times of mass to obtain a coating material, and carrying out deposition treatment on graphene and the coating material, wherein the mass-volume ratio between the graphene and the coating material is 30g: and (3) 10mL, and then placing for 12h at 80 ℃ under vacuum condition to obtain the lithium ion battery anode silicon-carbon composite material.
Comparative example 1
A preparation method of a silicon-carbon composite material of a lithium ion battery cathode,
the method comprises the following steps:
guanidine hydrochloride and ultrapure water are mixed according to the mass volume ratio of 12mg:2mL is mixed and dissolved, and a vortex machine is adopted for full oscillation to obtain a mixed solution; transferring the mixed solution into a hydrothermal synthesis reaction kettle with a polytetrafluoroethylene lining for reaction, heating to 160 ℃ by using an oven for reaction, controlling the reaction time to 6 hours to obtain a reaction solution, and cooling the reaction solution to room temperature after the reaction is finished; centrifuging the reaction solution at 10000rpm and 4deg.C for 30min, and collecting supernatant;
next, the collected supernatant was mixed with sodium acetate, hexadecylamine and sodium citrate, wherein the mass-to-volume ratio between the supernatant, sodium acetate, hexadecylamine and sodium citrate was 12mL:1g:0.5mL:0.2g, mixing uniformly at 200rpm for 2 hours at room temperature by a shaker until the solution is green, dialyzing the solution by using a dialysis membrane of 3000Da, recovering a retention solution, and dispersing the retention solution in 30mL of N, N-dimethylformamide solution to obtain a viscous compound;
finally, carrying out ultrasonic mixing on the obtained sticky compound, the modified carbon nano tube, the propylene glycol, the ferric chloride and the acetone, wherein the mass volume ratio of the sticky compound to the modified carbon nano tube to the propylene glycol to the ferric chloride to the acetone is 5g:0.1g:6mL:0.2g:10mL, wherein the power of ultrasound is 300W, the time of ultrasound is 1h, after ultrasound treatment, centrifugation is carried out for 10min at 2000rpm and 4 ℃, the tan precipitate is collected, the tan precipitate is resuspended in ethanol solution with five times mass to obtain a coating material, and graphene and the coating material are subjected to deposition treatment, wherein the mass-volume ratio between the graphene and the coating material is 20g:20mL, then placed under vacuum at 80℃for 12 h.
The preparation method of the lithium ion battery cathode silicon-carbon composite material,
the preparation method of the modified carbon nano tube comprises the following steps:
dispersing 0.1g of p-phenylenediamine and 50mg of carbon nano tube into 10mL of ammonia water with mass fraction of 10%, stirring and refluxing for 8h at 90 ℃, filtering by using a 0.22um microporous filter membrane, and finally drying in vacuum at 60 ℃ for 60min to obtain the nano-crystalline p-phenylenediamine.
The preparation method of the lithium ion battery cathode silicon-carbon composite material,
the carbon nanotubes were purchased from Guangdong Weng Jiang chemical agent Co., ltd, with CAS number 308068-56-6.
The preparation method of the lithium ion battery cathode silicon-carbon composite material,
the deposition treatment method is an electrochemical deposition method.
The preparation method of the lithium ion battery cathode silicon-carbon composite material,
the electrochemical deposition method is as follows:
and (3) taking ethanol solution containing a coating material as a working solution, graphene as a working electrode, and a platinum electrode as a counter electrode, and carrying out deposition treatment.
The preparation method of the lithium ion battery cathode silicon-carbon composite material,
wherein the mass volume ratio of the coating material in the working solution to the ethanol solution is 10g:200mL.
The preparation method of the lithium ion battery cathode silicon-carbon composite material,
the parameters of the electrochemical deposition method are as follows:
the time was 200min and the voltage was 5V.
Comparative example 2
A preparation method of a silicon-carbon composite material of a lithium ion battery cathode,
the method comprises the following steps:
urea, (3-aminopropyl) trimethoxysilane and ultrapure water were mixed in a mass volume ratio of 12mg:1mL:2mL is mixed and dissolved, and a vortex machine is adopted for full oscillation to obtain a mixed solution; transferring the mixed solution into a hydrothermal synthesis reaction kettle with a polytetrafluoroethylene lining for reaction, heating to 160 ℃ by using an oven for reaction, controlling the reaction time to 6 hours to obtain a reaction solution, and cooling the reaction solution to room temperature after the reaction is finished; centrifuging the reaction solution at 10000rpm and 4deg.C for 30min, and collecting supernatant;
next, the collected supernatant was mixed with sodium acetate, hexadecylamine and sodium citrate, wherein the mass-to-volume ratio between the supernatant, sodium acetate, hexadecylamine and sodium citrate was 12mL:1g:0.5mL:0.2g, mixing uniformly at 200rpm for 2 hours at room temperature by a shaker until the solution is green, dialyzing the solution by using a dialysis membrane of 3000Da, recovering a retention solution, and dispersing the retention solution in 30mL of N, N-dimethylformamide solution to obtain a viscous compound;
finally, carrying out ultrasonic mixing on the obtained sticky compound, the modified carbon nano tube, the propylene glycol, the ferric chloride and the acetone, wherein the mass volume ratio of the sticky compound to the modified carbon nano tube to the propylene glycol to the ferric chloride to the acetone is 5g:0.1g:6mL:0.2g:10mL, wherein the power of ultrasound is 300W, the time of ultrasound is 1h, after ultrasound treatment, centrifugation is carried out for 10min at 2000rpm and 4 ℃, the tan precipitate is collected, the tan precipitate is resuspended in ethanol solution with five times mass to obtain a coating material, and graphene and the coating material are subjected to deposition treatment, wherein the mass-volume ratio between the graphene and the coating material is 20g:20mL, then placed under vacuum at 80℃for 12 h.
The preparation method of the lithium ion battery cathode silicon-carbon composite material,
the preparation method of the modified carbon nano tube comprises the following steps:
dispersing 0.1g of p-phenylenediamine and 50mg of carbon nano tube into 10mL of ammonia water with mass fraction of 10%, stirring and refluxing for 8h at 90 ℃, filtering by using a 0.22um microporous filter membrane, and finally drying in vacuum at 60 ℃ for 60min to obtain the nano-crystalline p-phenylenediamine.
The preparation method of the lithium ion battery cathode silicon-carbon composite material,
the carbon nanotubes were purchased from Guangdong Weng Jiang chemical agent Co., ltd, with CAS number 308068-56-6.
The preparation method of the lithium ion battery cathode silicon-carbon composite material,
the deposition treatment method is an electrochemical deposition method.
The preparation method of the lithium ion battery cathode silicon-carbon composite material,
the electrochemical deposition method is as follows:
and (3) taking ethanol solution containing a coating material as a working solution, graphene as a working electrode, and a platinum electrode as a counter electrode, and carrying out deposition treatment.
The preparation method of the lithium ion battery cathode silicon-carbon composite material,
wherein the mass volume ratio of the coating material in the working solution to the ethanol solution is 10g:200mL.
The preparation method of the lithium ion battery cathode silicon-carbon composite material,
the parameters of the electrochemical deposition method are as follows:
the time was 200min and the voltage was 5V.
Comparative example 3
A preparation method of a silicon-carbon composite material of a lithium ion battery cathode,
the method comprises the following steps:
guanidine hydrochloride, (3-aminopropyl) trimethoxysilane and ultrapure water are mixed according to the mass volume ratio of 12mg:1mL:2mL is mixed and dissolved, and a vortex machine is adopted for full oscillation to obtain a mixed solution; transferring the mixed solution into a hydrothermal synthesis reaction kettle with a polytetrafluoroethylene lining for reaction, heating to 160 ℃ by using an oven for reaction, controlling the reaction time to 6 hours to obtain a reaction solution, and cooling the reaction solution to room temperature after the reaction is finished; centrifuging the reaction solution at 10000rpm and 4deg.C for 30min, and collecting supernatant;
next, the collected supernatant was mixed with sodium acetate, triethanolamine and sodium citrate, wherein the mass to volume ratio between the supernatant, sodium acetate, triethanolamine and sodium citrate was 12mL:1g:0.5mL:0.2g, mixing uniformly at 200rpm for 2 hours at room temperature by a shaker until the solution is green, dialyzing the solution by using a dialysis membrane of 3000Da, recovering a retention solution, and dispersing the retention solution in 30mL of N, N-dimethylformamide solution to obtain a viscous compound;
finally, carrying out ultrasonic mixing on the obtained sticky compound, the modified carbon nano tube, the propylene glycol, the ferric chloride and the acetone, wherein the mass volume ratio of the sticky compound to the modified carbon nano tube to the propylene glycol to the ferric chloride to the acetone is 5g:0.1g:6mL:0.2g:10mL, wherein the power of ultrasound is 300W, the time of ultrasound is 1h, after ultrasound treatment, centrifugation is carried out for 10min at 2000rpm and 4 ℃, the tan precipitate is collected, the tan precipitate is resuspended in ethanol solution with five times mass to obtain a coating material, and graphene and the coating material are subjected to deposition treatment, wherein the mass-volume ratio between the graphene and the coating material is 20g:20mL, then placed under vacuum at 80℃for 12 h.
The preparation method of the lithium ion battery cathode silicon-carbon composite material,
the preparation method of the modified carbon nano tube comprises the following steps:
dispersing 0.1g of p-phenylenediamine and 50mg of carbon nano tube into 10mL of ammonia water with mass fraction of 10%, stirring and refluxing for 8h at 90 ℃, filtering by using a 0.22um microporous filter membrane, and finally drying in vacuum at 60 ℃ for 60min to obtain the nano-crystalline p-phenylenediamine.
The preparation method of the lithium ion battery cathode silicon-carbon composite material,
the carbon nanotubes were purchased from Guangdong Weng Jiang chemical agent Co., ltd, with CAS number 308068-56-6.
The preparation method of the lithium ion battery cathode silicon-carbon composite material,
the deposition treatment method is an electrochemical deposition method.
The preparation method of the lithium ion battery cathode silicon-carbon composite material,
the electrochemical deposition method is as follows:
and (3) taking ethanol solution containing a coating material as a working solution, graphene as a working electrode, and a platinum electrode as a counter electrode, and carrying out deposition treatment.
The preparation method of the lithium ion battery cathode silicon-carbon composite material,
wherein the mass volume ratio of the coating material in the working solution to the ethanol solution is 10g:200mL.
The preparation method of the lithium ion battery cathode silicon-carbon composite material,
the parameters of the electrochemical deposition method are as follows:
the time was 200min and the voltage was 5V.
Comparative example 4
A preparation method of a silicon-carbon composite material of a lithium ion battery cathode,
the method comprises the following steps:
guanidine hydrochloride, (3-aminopropyl) trimethoxysilane and ultrapure water are mixed according to the mass volume ratio of 12mg:1mL:2mL is mixed and dissolved, and a vortex machine is adopted for full oscillation to obtain a mixed solution; transferring the mixed solution into a hydrothermal synthesis reaction kettle with a polytetrafluoroethylene lining for reaction, heating to 160 ℃ by using an oven for reaction, controlling the reaction time to 6 hours to obtain a reaction solution, and cooling the reaction solution to room temperature after the reaction is finished; centrifuging the reaction solution at 10000rpm and 4deg.C for 30min, and collecting supernatant;
next, the collected supernatant was mixed with sodium acetate, sodium cetyl amine, wherein the mass to volume ratio between the supernatant, sodium acetate, cetyl amine was 12mL:1g:0.5mL, mixing uniformly at 200rpm for 2h at room temperature by a shaker until the solution is green, dialyzing the solution by using a dialysis membrane of 3000Da, recovering the retentate, and dispersing the retentate in 30mL of N, N-dimethylformamide solution to obtain a viscous compound;
finally, carrying out ultrasonic mixing on the obtained sticky compound, the modified carbon nano tube, the propylene glycol, the ferric chloride and the acetone, wherein the mass volume ratio of the sticky compound to the modified carbon nano tube to the propylene glycol to the ferric chloride to the acetone is 5g:0.1g:6mL:0.2g:10mL, wherein the power of ultrasound is 300W, the time of ultrasound is 1h, after ultrasound treatment, centrifugation is carried out for 10min at 2000rpm and 4 ℃, the tan precipitate is collected, the tan precipitate is resuspended in ethanol solution with five times mass to obtain a coating material, and graphene and the coating material are subjected to deposition treatment, wherein the mass-volume ratio between the graphene and the coating material is 20g:20mL, then placed under vacuum at 80℃for 12 h.
The preparation method of the lithium ion battery cathode silicon-carbon composite material,
the preparation method of the modified carbon nano tube comprises the following steps:
dispersing 0.1g of p-phenylenediamine and 50mg of carbon nano tube into 10mL of ammonia water with mass fraction of 10%, stirring and refluxing for 8h at 90 ℃, filtering by using a 0.22um microporous filter membrane, and finally drying in vacuum at 60 ℃ for 60min to obtain the nano-crystalline p-phenylenediamine.
The preparation method of the lithium ion battery cathode silicon-carbon composite material,
the carbon nanotubes were purchased from Guangdong Weng Jiang chemical agent Co., ltd, with CAS number 308068-56-6.
The preparation method of the lithium ion battery cathode silicon-carbon composite material,
the deposition treatment method is an electrochemical deposition method.
The preparation method of the lithium ion battery cathode silicon-carbon composite material,
the electrochemical deposition method is as follows:
and (3) taking ethanol solution containing a coating material as a working solution, graphene as a working electrode, and a platinum electrode as a counter electrode, and carrying out deposition treatment.
The preparation method of the lithium ion battery cathode silicon-carbon composite material,
wherein the mass volume ratio of the coating material in the working solution to the ethanol solution is 10g:200mL.
The preparation method of the lithium ion battery cathode silicon-carbon composite material,
the parameters of the electrochemical deposition method are as follows:
the time was 200min and the voltage was 5V.
Comparative example 5
A preparation method of a silicon-carbon composite material of a lithium ion battery cathode,
the method comprises the following steps:
guanidine hydrochloride, (3-aminopropyl) trimethoxysilane and ultrapure water are mixed according to the mass volume ratio of 12mg:1mL:2mL is mixed and dissolved, and a vortex machine is adopted for full oscillation to obtain a mixed solution; transferring the mixed solution into a hydrothermal synthesis reaction kettle with a polytetrafluoroethylene lining for reaction, heating to 160 ℃ by using an oven for reaction, controlling the reaction time to 6 hours to obtain a reaction solution, and cooling the reaction solution to room temperature after the reaction is finished; centrifuging the reaction solution at 10000rpm and 4deg.C for 30min, and collecting supernatant;
next, the collected supernatant was mixed with sodium acetate, hexadecylamine and sodium citrate, wherein the mass-to-volume ratio between the supernatant, sodium acetate, hexadecylamine and sodium citrate was 12mL:1g:0.5mL:0.2g, mixing uniformly at 200rpm for 2 hours at room temperature by a shaker until the solution is green, dialyzing the solution by using a dialysis membrane of 3000Da, recovering a retention solution, and dispersing the retention solution in 30mL of N, N-dimethylformamide solution to obtain a viscous compound;
finally, carrying out ultrasonic mixing on the obtained sticky compound, the modified carbon nano tube, the propylene glycol and the acetone, wherein the mass volume ratio of the sticky compound to the modified carbon nano tube to the propylene glycol to the acetone is 5g:0.1g:6mL:10mL, wherein the power of ultrasound is 300W, the time of ultrasound is 1h, after ultrasound treatment, centrifugation is carried out for 10min at 2000rpm and 4 ℃, the tan precipitate is collected, the tan precipitate is resuspended in ethanol solution with five times mass to obtain a coating material, and graphene and the coating material are subjected to deposition treatment, wherein the mass-volume ratio between the graphene and the coating material is 20g:20mL, then placed under vacuum at 80℃for 12 h.
The preparation method of the lithium ion battery cathode silicon-carbon composite material,
the preparation method of the modified carbon nano tube comprises the following steps:
dispersing 0.1g of p-phenylenediamine and 50mg of carbon nano tube into 10mL of ammonia water with mass fraction of 10%, stirring and refluxing for 8h at 90 ℃, filtering by using a 0.22um microporous filter membrane, and finally drying in vacuum at 60 ℃ for 60min to obtain the nano-crystalline p-phenylenediamine.
The preparation method of the lithium ion battery cathode silicon-carbon composite material,
the carbon nanotubes were purchased from Guangdong Weng Jiang chemical agent Co., ltd, with CAS number 308068-56-6.
The preparation method of the lithium ion battery cathode silicon-carbon composite material,
the deposition treatment method is an electrochemical deposition method.
The preparation method of the lithium ion battery cathode silicon-carbon composite material,
the electrochemical deposition method is as follows:
and (3) taking ethanol solution containing a coating material as a working solution, graphene as a working electrode, and a platinum electrode as a counter electrode, and carrying out deposition treatment.
The preparation method of the lithium ion battery cathode silicon-carbon composite material,
wherein the mass volume ratio of the coating material in the working solution to the ethanol solution is 10g:200mL.
The preparation method of the lithium ion battery cathode silicon-carbon composite material,
the parameters of the electrochemical deposition method are as follows:
the time was 200min and the voltage was 5V.
Comparative example 6
A preparation method of a silicon-carbon composite material of a lithium ion battery cathode,
the method comprises the following steps:
guanidine hydrochloride, (3-aminopropyl) trimethoxysilane and ultrapure water are mixed according to the mass volume ratio of 12mg:1mL:2mL is mixed and dissolved, and a vortex machine is adopted for full oscillation to obtain a mixed solution; transferring the mixed solution into a hydrothermal synthesis reaction kettle with a polytetrafluoroethylene lining for reaction, heating to 160 ℃ by using an oven for reaction, controlling the reaction time to 6 hours to obtain a reaction solution, and cooling the reaction solution to room temperature after the reaction is finished; centrifuging the reaction solution at 10000rpm and 4deg.C for 30min, and collecting supernatant;
next, the collected supernatant was mixed with sodium acetate, hexadecylamine and sodium citrate, wherein the mass-to-volume ratio between the supernatant, sodium acetate, hexadecylamine and sodium citrate was 12mL:1g:0.5mL:0.2g, mixing uniformly at 200rpm for 2 hours at room temperature by a shaker until the solution is green, dialyzing the solution by using a dialysis membrane of 3000Da, recovering a retention solution, and dispersing the retention solution in 30mL of N, N-dimethylformamide solution to obtain a viscous compound;
finally, carrying out ultrasonic mixing on the obtained sticky compound, the modified carbon nano tube, the ferric chloride and the acetone, wherein the mass volume ratio of the sticky compound to the modified carbon nano tube to the propylene glycol to the ferric chloride to the acetone is 5g:0.1g:2g:10mL, wherein the power of ultrasound is 300W, the time of ultrasound is 1h, after ultrasound treatment, centrifugation is carried out for 10min at 2000rpm and 4 ℃, the tan precipitate is collected, the tan precipitate is resuspended in ethanol solution with five times mass to obtain a coating material, and graphene and the coating material are subjected to deposition treatment, wherein the mass-volume ratio between the graphene and the coating material is 20g:20mL, then placed under vacuum at 80℃for 12 h.
The preparation method of the lithium ion battery cathode silicon-carbon composite material,
the preparation method of the modified carbon nano tube comprises the following steps:
dispersing 0.1g of p-phenylenediamine and 50mg of carbon nano tube into 10mL of ammonia water with mass fraction of 10%, stirring and refluxing for 8h at 90 ℃, filtering by using a 0.22um microporous filter membrane, and finally drying in vacuum at 60 ℃ for 60min to obtain the nano-crystalline p-phenylenediamine.
The preparation method of the lithium ion battery cathode silicon-carbon composite material,
the carbon nanotubes were purchased from Guangdong Weng Jiang chemical agent Co., ltd, with CAS number 308068-56-6.
The preparation method of the lithium ion battery cathode silicon-carbon composite material,
the deposition treatment method is an electrochemical deposition method.
The preparation method of the lithium ion battery cathode silicon-carbon composite material,
the electrochemical deposition method is as follows:
and (3) taking ethanol solution containing a coating material as a working solution, graphene as a working electrode, and a platinum electrode as a counter electrode, and carrying out deposition treatment.
The preparation method of the lithium ion battery cathode silicon-carbon composite material,
wherein the mass volume ratio of the coating material in the working solution to the ethanol solution is 10g:200mL.
The preparation method of the lithium ion battery cathode silicon-carbon composite material,
the parameters of the electrochemical deposition method are as follows:
the time was 200min and the voltage was 5V.
Application examples
The products prepared in examples 1-3 and comparative examples 1-6 were selected for testing:
reference is made to the patent, application number, for better comparison, using the scheme of its test: CN202310871436.7, specification 0123-0130, is subjected to a test of capacity retention of 100 cycles/500 cycles, wherein the initial capacity of the battery is 20000mAH, wherein the capacity retention before cycling is 100%.
Table 1 test results
Comparative examples 1 to 6 were subjected to experiments concerning deletion, restriction, and the like with respect to example 1. For example, comparative example 1 lacks a substance such as (3-aminopropyl) trimethoxysilane, which contains a silicon atom and is a silicon coupling agent capable of participating in the coupling of materials under the action of a reducing agent to enhance electron hole effect; in the comparative example 2, guanidine hydrochloride is replaced by urea, the effect of the urea is far less than that of guanidine hydrochloride, the guanidine hydrochloride can enhance the compactness of the crystal structure of the composite material, and meanwhile, the guanidine hydrochloride also participates in the formation of a novel photoelectric carbon point material with (3-aminopropyl) trimethoxysilane under the action of a reducing agent; in comparative example 3, triethanolamine is used, and the effect of the triethanolamine on supplementing the surface or internal defect structure of the composite material is poor, so that the electron transfer on the surface or the inside of the material is affected to a certain extent; comparative examples 4-6 were removed with hexadecylamine, ferric chloride, and propylene glycol, respectively, which also greatly affected the conductivity and overall battery performance.
In summary, the invention innovatively designs a silicon-carbon composite material based on (3-aminopropyl) trimethoxysilane, guanidine hydrochloride and modified carbon nano tube as main bodies, and assists a plurality of comprehensively obtained composite materials such as hexadecylamine, sodium citrate potassium as reducing agent and the like, and the materials are synergistic mutually to promote the recyclable capacity of the lithium battery; meanwhile, the silane coupling agent and the conductive carbon nano tube are combined for the first time, so that effective conductive cycle times are achieved; in addition, it is supposed that ferric chloride and the like play a role in protecting the lithium battery, bring a certain heat dissipation effect and maintain the overall efficiency of the lithium battery. The silicon-carbon composite material is beneficial to effective migration of lithium ions, avoids concentration of lithium ions and stress accumulation, causes less migration quantity of effective lithium ions, and further has low actual capacity, and hexadecylamine can meet the safety of a cathode material, and particularly, the hexadecylamine is wrapped on the surface of graphene.
The invention and its embodiments have been described above by way of illustration and not limitation, and the actual construction is not limited to this. Therefore, if one of ordinary skill in the art is informed by this disclosure, the structural mode and the embodiments similar to the technical scheme are not creatively designed without departing from the gist of the present invention.
Claims (6)
1. A preparation method of a lithium ion battery cathode silicon-carbon composite material is characterized in that,
the method comprises the following steps:
guanidine hydrochloride, (3-aminopropyl) trimethoxysilane and ultrapure water are mixed according to the mass volume ratio (6 mg-20 mg): (0.2 mL-3 mL): (1 mL-5 mL) and mixing and dissolving, and fully oscillating by a vortex machine to obtain a mixed solution; transferring the mixed solution into a hydrothermal synthesis reaction kettle with a polytetrafluoroethylene lining for reaction, heating to 140-180 ℃ by using an oven for reaction, controlling the reaction time to 6 hours to obtain a reaction solution, and cooling the reaction solution to room temperature after the reaction is finished; centrifuging the reaction solution, and collecting supernatant;
next, the collected supernatant was mixed with sodium acetate, hexadecylamine and sodium citrate, wherein the mass-to-volume ratio between the supernatant, sodium acetate, hexadecylamine and sodium citrate was (10 mL-15 mL): (0.5 g-3 g): (0.1 mL-1 mL): (0.1 g-0.6 g), mixing at 200rpm for 2h at room temperature, dialyzing the solution with 3000Da dialysis membrane, recovering the retentate, and dispersing in 30mL of N, N-dimethylformamide solution to obtain viscous compound;
finally, the obtained sticky compound is evenly mixed with the modified carbon nano tube, the propylene glycol, the ferric chloride and the acetone by ultrasonic, wherein the mass volume ratio of the sticky compound to the modified carbon nano tube to the propylene glycol to the ferric chloride to the acetone is (2 g-10 g): 0.1g:6mL:0.2g:10mL, collecting a tan precipitate, re-suspending the tan precipitate in ethanol solution with five times mass to obtain a coating material, and carrying out deposition treatment on graphene and the coating material, wherein the mass-volume ratio between the graphene and the coating material is (10 g-30 g): (10 mL-30 mL), and then placing for 12h at 80 ℃ under vacuum condition to obtain the lithium ion battery anode silicon-carbon composite material.
2. The method for preparing the lithium ion battery anode silicon-carbon composite material according to claim 1, wherein,
the preparation method of the modified carbon nano tube comprises the following steps:
dispersing 0.1g of p-phenylenediamine and 50mg of carbon nano tube into 10mL of ammonia water with mass fraction of 10%, stirring and refluxing for 8h at 90 ℃, filtering by using a 0.22um microporous filter membrane, and finally drying in vacuum at 60 ℃ for 60min to obtain the modified carbon nano tube.
3. The method for preparing the lithium ion battery anode silicon-carbon composite material according to claim 1, wherein,
the deposition treatment method is an electrochemical deposition method.
4. The method for preparing the lithium ion battery anode silicon-carbon composite material according to claim 3, wherein,
the electrochemical deposition method is as follows:
and (3) taking ethanol solution containing a coating material as a working solution, graphene as a working electrode, and a platinum electrode as a counter electrode, and carrying out deposition treatment.
5. The method for preparing the lithium ion battery anode silicon-carbon composite material according to claim 4, wherein,
wherein the mass volume ratio of the coating material in the working solution to the ethanol solution is 10g:200mL.
6. The method for preparing the lithium ion battery anode silicon-carbon composite material according to claim 5, wherein,
the parameters of the electrochemical deposition method are as follows:
the time was 200min and the voltage was 5V.
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