CN117186416A - Silicon-carbon copolymer, preparation method thereof and application thereof in battery anode material - Google Patents
Silicon-carbon copolymer, preparation method thereof and application thereof in battery anode material Download PDFInfo
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- CN117186416A CN117186416A CN202311158773.8A CN202311158773A CN117186416A CN 117186416 A CN117186416 A CN 117186416A CN 202311158773 A CN202311158773 A CN 202311158773A CN 117186416 A CN117186416 A CN 117186416A
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000010405 anode material Substances 0.000 title abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 113
- 229920002379 silicone rubber Polymers 0.000 claims abstract description 90
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 85
- 239000003054 catalyst Substances 0.000 claims abstract description 76
- 239000000178 monomer Substances 0.000 claims abstract description 43
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 39
- 239000010703 silicon Substances 0.000 claims abstract description 38
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910018131 Al-Mn Inorganic materials 0.000 claims abstract description 34
- 229910018461 Al—Mn Inorganic materials 0.000 claims abstract description 34
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims description 46
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 43
- 239000011889 copper foil Substances 0.000 claims description 43
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 36
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 35
- 238000005303 weighing Methods 0.000 claims description 28
- 239000001257 hydrogen Substances 0.000 claims description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 24
- 229920002545 silicone oil Polymers 0.000 claims description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 21
- 229910052799 carbon Inorganic materials 0.000 claims description 21
- 239000005051 trimethylchlorosilane Substances 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 15
- 239000011261 inert gas Substances 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 230000002194 synthesizing effect Effects 0.000 claims description 14
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 claims description 13
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 239000004945 silicone rubber Substances 0.000 claims description 12
- 229920001971 elastomer Polymers 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 11
- 239000005060 rubber Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 9
- 229910001416 lithium ion Inorganic materials 0.000 claims description 9
- JOOMLFKONHCLCJ-UHFFFAOYSA-N N-(trimethylsilyl)diethylamine Chemical compound CCN(CC)[Si](C)(C)C JOOMLFKONHCLCJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 8
- 239000005457 ice water Substances 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- 239000007773 negative electrode material Substances 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- OTYYBJNSLLBAGE-UHFFFAOYSA-N CN1C(CCC1)=O.[N] Chemical compound CN1C(CCC1)=O.[N] OTYYBJNSLLBAGE-UHFFFAOYSA-N 0.000 claims description 6
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 6
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 6
- 239000006230 acetylene black Substances 0.000 claims description 6
- 230000003213 activating effect Effects 0.000 claims description 6
- 238000007605 air drying Methods 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 239000000498 cooling water Substances 0.000 claims description 6
- 238000007872 degassing Methods 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 239000012065 filter cake Substances 0.000 claims description 6
- 238000007710 freezing Methods 0.000 claims description 6
- 230000008014 freezing Effects 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 229940099607 manganese chloride Drugs 0.000 claims description 6
- 235000002867 manganese chloride Nutrition 0.000 claims description 6
- 239000011565 manganese chloride Substances 0.000 claims description 6
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 claims description 6
- 239000004570 mortar (masonry) Substances 0.000 claims description 6
- 230000000379 polymerizing effect Effects 0.000 claims description 6
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- 239000010453 quartz Substances 0.000 claims description 6
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- 238000000967 suction filtration Methods 0.000 claims description 6
- 238000009489 vacuum treatment Methods 0.000 claims description 6
- 238000005194 fractionation Methods 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 20
- 239000005543 nano-size silicon particle Substances 0.000 abstract description 14
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract description 12
- 238000009835 boiling Methods 0.000 abstract description 12
- 238000000859 sublimation Methods 0.000 abstract description 12
- 230000008022 sublimation Effects 0.000 abstract description 12
- 239000000945 filler Substances 0.000 abstract description 10
- 238000004073 vulcanization Methods 0.000 abstract description 7
- 230000003993 interaction Effects 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 24
- 238000011068 loading method Methods 0.000 description 11
- -1 polysiloxane Polymers 0.000 description 10
- 238000000034 method Methods 0.000 description 8
- 239000010406 cathode material Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- 239000003431 cross linking reagent Substances 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229920001558 organosilicon polymer Polymers 0.000 description 6
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical compound C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 description 5
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 5
- 239000004205 dimethyl polysiloxane Substances 0.000 description 5
- 230000003301 hydrolyzing effect Effects 0.000 description 5
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 5
- 239000002861 polymer material Substances 0.000 description 5
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- HIYJCTIYKIUGET-UHFFFAOYSA-N C[SiH](C)C.C(C)NCC Chemical compound C[SiH](C)C.C(C)NCC HIYJCTIYKIUGET-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 description 3
- ZTHXGSSBOFYPTH-UHFFFAOYSA-N N-ethyl-N-methylsilylethanamine Chemical compound CCN(CC)[SiH2]C ZTHXGSSBOFYPTH-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 230000003100 immobilizing effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 2
- 229910018540 Si C Inorganic materials 0.000 description 1
- 241000519995 Stachys sylvatica Species 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
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- 229920003023 plastic Polymers 0.000 description 1
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- 230000008569 process Effects 0.000 description 1
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- 229910010271 silicon carbide Inorganic materials 0.000 description 1
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- 239000002210 silicon-based material Substances 0.000 description 1
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- Catalysts (AREA)
Abstract
The invention discloses a silicon-carbon copolymer and a preparation method and application thereof. Firstly, activated carbon immobilized aluminum chloride is selected, and manganese element is doped to prepare a catalyst Al-Mn/C, so that the sublimation point and boiling point of the aluminum chloride are changed, and the stability of the aluminum chloride catalyst immobilized by the activated carbon is improved. The modified aluminum chloride prepared by the invention is used for preparingAfter the monomer organosilicon, the yield and purity of the monomer organosilicon are increased. Then select SiO 2 As modified filler, the 107 silicon rubber is modified and doped with molybdenum element, and after vulcanization at room temperature, the 107 silicon rubber has excellent high temperature resistance and dielectric property. In addition, the doping of nano silicon dioxide can improve the conductivity of 107 silicon rubber, and the silicon-carbon copolymer obtained through interaction with monomer organic silicon has a three-dimensional porous structure, so that the silicon-carbon copolymer has wide application prospect in the field of battery anode materials.
Description
Technical Field
The invention belongs to the technical field of organic silicon synthesis, relates to a silicon-carbon copolymer, and in particular relates to a silicon-carbon copolymer and a preparation method and application thereof.
Background
Compared with the traditional carbon-based polymer material, the high bond energy and the large bond angle of the silicon-oxygen bond in the molecular skeleton structure of the organic silicon polymer material lead the organic silicon polymer material to have the advantages of more outstanding high and low temperature resistance, aging resistance, low temperature flexibility and the like, and are widely applied to various industries of national economy. However, the general polarity of the molecular chain is low, the interaction is relatively weak, and the mechanical strength such as the tensile strength, the low tearing strength and the like of the pure organosilicon polymer material limit the application of the pure organosilicon polymer material. On one hand, the mechanical strength of the material can be improved by adding the reinforcing filler through physical blending, but the material is limited by non-molecular scale improvement, and the lifting effect is limited. On the other hand, the molecular chain of the carbon-based polymer with the characteristics of traditional high strength can be introduced into the organic silicon chain segment by utilizing the block chemical reaction to form the organic silicon carbon block copolymer, which is one of the important methods for modifying the organic silicon materials currently being developed. The organosilicon carbon block copolymer is a hybrid containing both organosilicon polymer chain segments and organosilicon carbon polymer chain segments, and becomes a novel high molecular material based on the characteristics of organosilicon polymers and the general properties of organosilicon carbon polymers.
Organosilicon compounds are compounds in which the Si-C bond is present and at least one substituent is directly bonded to a silicon atom. Silicone oil, silicone rubber, silicone resin and silane coupling agent can be used as most important types of organic silicon, the former three types are changed into polysiloxane by polycondensation after dimethyl dichlorosilane is hydrolyzed, the polysiloxane is synthesized with a cross-linking agent, a sealing agent and the like, the silicone oil, the silicone rubber, the silicone resin and the silane coupling agent are currently considered to be relatively accurate products of the organic silicon, the silane coupling agent is not polymer, and the silane coupling agent is mainly used as a coupling agent, and can be added in a small amount in order to improve the problem of interconnection of inorganic matters in plastics. Preparation of organosilicon carbon copolymers the most important and most useful organosilicon monomers, methyl chlorosilane, are currently considered to be the backbone and foundation of the entire organosilicon industry, are independent of the organosilicon monomers. Because the production process of methylchlorosilanes is relatively complex and the technical difficulty is relatively high, and the methylchlorosilanes belongs to the technical intensive industry, the level of methylchlorosilanes and the device for preparing methylchlorosilanes are often used as a national organosilicon industry development standard.
The silicon-carbon copolymer prepared by the invention can be widely applied to the field of battery cathode materials. Aluminum trichloride is selected as a catalyst, and the catalyst has the advantages of wide effect, low price and good catalytic effect, but the aluminum trichloride is modified by considering the temperature condition required by the preparation of the organic silicon monomer. The 107 silicon rubber is a synthetic silicon-carbon copolymer raw material, the nano silicon dioxide is an ultrafine nano-scale material, the chemical resistance, ageing resistance and conductivity of the material can be improved, no pollution is caused, the 107 silicon rubber is modified by using the nano silicon dioxide as a filler, and finally the silicon-carbon copolymer with a three-dimensional porous structure is obtained.
Disclosure of Invention
Aiming at the problems, the invention firstly selects the activated carbon immobilized aluminum chloride catalyst and introduces manganese element, and then selects SiO 2 As modified filler for modifying 107 silicon rubber, molybdenum element is doped, and finally, the silicon-carbon copolymer obtained through interaction with monomer organic silicon has a three-dimensional porous structure, can be applied to the field of battery anode materials, and has wide application prospects. The specific operation process of the invention is as follows:
s1, preparation of an Al-Mn/C catalyst: 23-33 g AlCl is added into a three-necked flask 3 And a small amount of absolute ethyl alcohol to be completely dissolved, then 65-94 g of active carbon is added into a reflux condensing tube to be heated and refluxed for 0.5 h, and then the active carbon is washed with a small amount of absolute ethyl alcohol for three times for suction filtration and air drying, and then a filter cake and manganese chloride are added according to the mass ratio of 10:1 in a mortar for 30min, and then put into a quartz bottle of 100 ml, and microwaved in a household microwave oven for 100 seconds. And then taking out, activating for 2-3 hours in an oven at 100-150 ℃, and then placing the activated carbon and manganese element supported aluminum chloride catalyst Al-Mn/C in a dryer for cooling to obtain the activated carbon and manganese element supported aluminum chloride catalyst Al-Mn/C. In this step AlCl 3 The sublimation point of (2) is 177.8 ℃, the boiling point is 182.7 ℃, and the reaction temperature of the monomer organosilicon prepared by the invention exceeds AlCl 3 The sublimation point of the aluminum chloride is improved by using the high boiling point of the activated carbon and the activated carbon-supported aluminum chloride. And it was also found that after the microwaves, the addition of manganese element filled the pore size of the activated carbon, and a catalyst scan occurredThe stability of the catalyst of the immobilized aluminum chloride is obviously improved by changing.
S2, synthesizing monomer organic silicon: and (2) purging the 2000L high-pressure reaction kettle with nitrogen to remove static air, firstly weighing 110-200 g of trimethylsilyl diethylamine, adding into the reaction kettle, secondly weighing 70-100 g of monomethyl hydrogen dichlorosilane, finally weighing 6-10 g of modified catalyst Al-Mn/C prepared in the step (S1), pouring into the reaction kettle, rapidly sealing the reaction kettle, adjusting the reaction temperature to 200-300 ℃, reacting for 2-3 hours, removing a heating device, opening kettle cooling water, cooling to 10-25 ℃, taking out liquid in the kettle, adding into a three-mouth bottle for fractionation, and collecting fraction trimethylchlorosilane at 50-65 ℃. In the step, raw materials adopt methylsilane-based diethylamine and methylhydrogen dichlorosilane, a distillation product is trimethylchlorosilane at 50-65 ℃ in the distillation process, and the added activated carbon is used for immobilizing aluminum chloride and doping manganese element to obtain a catalyst Al-Mn/C, so that the conversion rate of the trimethylsilane-based diethylamine is increased.
S3, modified 107 silicon rubber: weighing 107 silicon rubber, nickel nitrate and hydrogen-containing silicone oil, putting the 107 silicon rubber, nickel nitrate and hydrogen-containing silicone oil into a beaker with the ice-water bath temperature of 0-4 ℃, wherein the mass ratio of the 107 silicon rubber to the catalyst nickel to the hydrogen-containing silicone oil is 40:9:13, adopting a multifunctional dispersing machine to disperse nano SiO 2 The mass ratio of the rubber to the mixed rubber is 1:56 are thoroughly stirred and applied until the resulting composite is well mixed. Transferring to a vacuum drying oven for vacuum treatment at room temperature, transferring to a flat vulcanizing machine at 120 ℃ and 15 MPa, vulcanizing for 10-20 min, and then mixing the vulcanized product with molybdenum chloride according to the mass ratio of 10:1 into ethanol, the mixture was stirred in an ultrasonic cell for 30 minutes, followed by further stirring with a magnetic stirrer overnight. And washing the mixture for a plurality of times after drying, and centrifugally drying the mixture at 60 ℃ to obtain the modified 107 silicone rubber. In the step, 107 silicon rubber is chemically named as hydroxyl-terminated polydimethylsiloxane, nickel nitrate is used as a catalyst, the catalyst and cross-linking agent hydrogen-containing silicone oil are added and fully stirred, and then nano SiO is adopted 2 As modified filler, molybdenum element doping is carried out, so that 107 silicon rubber has excellent high temperature resistance and dielectric property after vulcanization at room temperature, the conductivity of 107 silicon rubber can be improved by doping nano silicon dioxide, and carbon prepared in step S4And (3) synthesizing the silicon-carbon copolymer by the silicon copolymer and the monomer organic silicon prepared in the step S2.
S4, synthesizing a silicon-carbon copolymer: dissolving the monomer organic silicon prepared in the step S2 and the 107 silicon rubber prepared in the step S3 in N, N-Dimethylformamide (DMF), wherein the mass ratio of the monomer organic silicon to the 107 silicon rubber modified in the step S3 to the DMF is 10:9: and (21) repeatedly freezing and degassing for five times by using liquid nitrogen, polymerizing for 20-30 hours under the protection of inert gas Ar, transferring to a clean crucible, placing into a tubular furnace, and calcining for 2 hours under the protection of inert gas Ar at the temperature of 150-350 ℃ to obtain the solid silicon-carbon copolymer. The step is a preparation process of the silicon-carbon copolymer, wherein the monomer organic silicon is trimethylchlorosilane, the step S3 is used for preparing the silicon-carbon copolymer by hydrolyzing the modified 107 silicon rubber, the trimethylchlorosilane and the DMF, the doping of the nano silicon dioxide is used for improving the conductivity of the 107 silicon rubber, and the prepared silicon-carbon copolymer is of a three-dimensional porous structure and has wide application prospect in the field of battery cathode materials.
S5, preparing an electrode plate and assembling a battery: weighing the silicon-carbon copolymer prepared in the step S4: acetylene black: the mass ratio of the binder is 7:2:1, fully grinding and refining the mixture, placing the mixture in a beaker, adding nitrogen methyl pyrrolidone, carrying out electromagnetic stirring for 12 hours, taking a piece of copper foil, scrubbing the copper foil with absolute ethyl alcohol, pouring the prepared slurry on the copper foil, uniformly scraping the copper foil by a scraper, drying the copper foil in a blast drying oven at 60 ℃ for 12 hours, taking the copper foil as a negative electrode material of a lithium ion battery after punching a raw sheet, taking a pure lithium sheet as a positive electrode, assembling the copper foil into a CR2032 button battery in a glove box filled with argon, and measuring the electrochemical performance of the CR2032 button battery.
Preferably: in the step S1, 100 g AlCl is added into a three-necked flask 3 ；
Preferably: adding 40 g active carbon in the step S1;
preferably: in the step S2, the trimethylsilyl diethylamine 110 and g are weighed and added into a reaction kettle;
preferably: in the step S2, the monomethyl hydrogen dichlorosilane 70 and g are weighed;
preferably: the temperature of the ice water bath in the step S3 is 2 ℃;
preferably: the vulcanizing time in the step S3 is 10 min;
preferably: the step S4 is carried out under the protection of inert gas Ar for polymerization of 20 h;
by adopting the technical scheme, the invention has the technical advantages that:
1. according to the preparation method, the silicon-carbon copolymer is prepared, the activated carbon is selected to carry the aluminum chloride and doped with manganese element to obtain the catalyst Al-Mn/C, the sublimation point and the boiling point of the aluminum chloride are changed, the catalytic activity of the aluminum chloride carried by the activated carbon is increased, and the conversion rate of reaction raw materials is increased after the catalyst is used for preparing monomer organosilicon.
2. The invention selects nano SiO 2 As modified filler and molybdenum element is introduced to modify 107 silicon rubber, the 107 silicon rubber has excellent high temperature resistance and dielectric property after vulcanization at room temperature. And (2) synthesizing the carbon-silicon copolymer by interaction of the modified 107 silicon rubber and the monomer organic silicon prepared in the step (S2).
3. The nano silicon dioxide doping can improve the conductivity of 107 silicon rubber, and the silicon-carbon copolymer obtained by interaction with monomer organic silicon has a three-dimensional porous structure, can be applied to the field of battery anode materials, and has wide application prospect.
4. The invention uses nano SiO 2 As modified filler, the modified 107 silicon rubber has the advantages of more outstanding high and low temperature resistance, aging resistance, low temperature flexibility and the like, and can be widely applied to various industries of national economy.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments or the description of the prior art will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is an SEM image of activated carbon.
FIG. 2 shows AlCl supported on activated carbon in example 1 of the present invention 3 SEM images of (a).
FIG. 3 is an SEM image of the catalyst Al-Mn/C of example 1 of the present invention.
FIG. 4 is a graph showing the effect of the catalysts prepared in example 2, comparative example 1 and comparative example 2 of the present invention on the reaction stability of methylsilyl diethylamine.
Fig. 5 is an SEM image of a silicon carbon copolymer material of example 4 of the present invention.
Fig. 6 is a graph of the cycling performance of the inventive example 4 silicon carbon copolymer assembled lithium battery and the comparative example 4 commercial lithium battery tested on a blue electrical tester.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved by the present invention more clear, the present invention is further described in detail below with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the present patent.
Example 1: s1, preparation of an Al-Mn/C catalyst: into a three-necked flask was charged 23 g AlCl 3 Dissolving with a small amount of absolute ethanol, adding 65 g active carbon, loading into reflux condenser, and heating and refluxing for 0.5. 0.5 h to obtain AlCl 3 Fully adsorbing the mixture on the surface of active carbon with the loading capacity of 35%, washing the mixture with a small amount of absolute ethyl alcohol for three times, carrying out suction filtration, carrying out air drying, and then mixing a filter cake and manganese chloride according to the mass ratio of 10:1 in a mortar for 30min, and then put into a quartz bottle of 100 ml, and microwaved in a household microwave oven for 100 seconds. And then taking out, activating 2h in a baking oven at the temperature of 100 ℃, and then placing the activated carbon and manganese element supported aluminum chloride catalyst Al-Mn/C in a dryer for cooling to obtain the activated carbon and manganese element supported aluminum chloride catalyst Al-Mn/C. In this step AlCl 3 The sublimation point of (2) is 177.8 ℃, the boiling point is 182.7 ℃, and the reaction temperature of the monomer organosilicon prepared by the invention exceeds AlCl 3 The sublimation point of the aluminum chloride is improved by using the high boiling point of the activated carbon and the activated carbon-supported aluminum chloride. And it has also been found that after the microwave, the pore diameter of the activated carbon is filled by the addition of manganese element, the scanning pattern of the catalyst is also changed, and the stability of the immobilized aluminum chloride catalyst is obviousAnd increases.
S2, synthesizing monomer organic silicon: purging a 2000L high-pressure reaction kettle with nitrogen to remove static air, firstly weighing trimethylsilyl diethylamine 110 g, adding into the reaction kettle, secondly weighing monomethyl hydrogen dichlorosilane 70 g, finally weighing the modified catalyst Al-Mn/C6 g prepared in the step S1, pouring into the reaction kettle, rapidly sealing the reaction kettle, regulating the reaction temperature to 200 ℃, reacting 2h, removing a heating device, opening kettle cooling water, cooling to 10 ℃, taking out the liquid in the kettle, adding into a three-mouth bottle for fractionation, and collecting fraction trimethylchlorosilane at 50 ℃. In the step, methylsilane-based diethylamine and methylhydrogen dichlorosilane are adopted as raw materials, trimethylchlorosilane is distilled at 50 ℃ in the distillation process, and activated carbon is added to carry aluminum chloride and doped with manganese element to obtain a catalyst Al-Mn/C, so that the conversion rate of trimethylsilane-based diethylamine is increased.
S3, modified 107 silicon rubber: weighing 107 silicon rubber, nickel nitrate and hydrogen-containing silicone oil, putting the 107 silicon rubber, nickel catalyst and the hydrogen-containing silicone oil into a beaker with the ice-water bath temperature of 0 ℃, wherein the mass ratio of the 107 silicon rubber to the nickel catalyst to the hydrogen-containing silicone oil is 40:9:13, adopting a multifunctional dispersing machine to disperse nano SiO 2 The mass ratio of the rubber to the mixed rubber is 1:56 are thoroughly stirred and applied until the resulting composite is well mixed. Transferring to a vacuum drying oven for vacuum treatment at room temperature, transferring to a plate vulcanizing machine at 120 ℃ and 15 MPa, vulcanizing for 10 min, and then mixing the vulcanized product with molybdenum chloride according to the mass ratio of 10:1 into ethanol, the mixture was stirred in an ultrasonic cell for 30 minutes, followed by further stirring with a magnetic stirrer overnight. And washing the mixture for a plurality of times after drying, and centrifugally drying the mixture at 60 ℃ to obtain the modified 107 silicone rubber. In the step, 107 silicon rubber is chemically named as hydroxyl-terminated polydimethylsiloxane, nickel nitrate is used as a catalyst, the catalyst and cross-linking agent hydrogen-containing silicone oil are added and fully stirred, and then nano SiO is adopted 2 As modified filler, molybdenum element doping is carried out, so that the 107 silicon rubber has excellent high temperature resistance and dielectric property after vulcanization at room temperature, the conductivity of the 107 silicon rubber can be improved by doping nano silicon dioxide, and the silicon-carbon copolymer prepared in the step S4 and the monomer organic silicon synthesized silicon-carbon copolymer prepared in the step S2 are synthesized.
S4, synthesizing a silicon-carbon copolymer: dissolving the monomer organic silicon prepared in the step S2 and the 107 silicon rubber prepared in the step S3 in N, N-Dimethylformamide (DMF), wherein the mass ratio of the monomer organic silicon to the 107 silicon rubber modified in the step S3 to the DMF is 10:9:21, repeatedly freezing and degassing for five times by liquid nitrogen, polymerizing 20 h under the protection of inert gas Ar, transferring into a clean crucible, placing into a tube furnace, calcining for 2 hours under the protection of inert gas Ar at the temperature of 150 ℃, and obtaining the solid silicon-carbon copolymer. The step is a preparation process of the silicon-carbon copolymer, wherein the monomer organic silicon is trimethylchlorosilane, the step S3 is used for preparing the silicon-carbon copolymer by hydrolyzing the modified 107 silicon rubber, the trimethylchlorosilane and the DMF, the doping of the nano silicon dioxide is used for improving the conductivity of the 107 silicon rubber, and the prepared silicon-carbon copolymer is of a three-dimensional porous structure and has wide application prospect in the field of battery cathode materials.
S5, preparing an electrode plate and assembling a battery: weighing the silicon-carbon copolymer prepared in the step S4: acetylene black: the mass ratio of the binder is 7:2:1, fully grinding and refining the mixture, placing the mixture in a beaker, adding nitrogen methyl pyrrolidone, carrying out electromagnetic stirring for 12 hours, taking a piece of copper foil, scrubbing the copper foil with absolute ethyl alcohol, pouring the prepared slurry on the copper foil, uniformly scraping the copper foil by a scraper, drying the copper foil in a blast drying oven at 60 ℃ for 12 hours, taking the copper foil as a negative electrode material of a lithium ion battery after punching a raw sheet, taking a pure lithium sheet as a positive electrode, assembling the copper foil into a CR2032 button battery in a glove box filled with argon, and measuring the electrochemical performance of the CR2032 button battery.
FIGS. 1-2 are respectively active carbon and active carbon-immobilized AlCl of example 1 of the present invention 3 SEM images of (a). As can be seen from the figure, the surface of the activated carbon is dull, uneven, and has many small holes. After loading aluminum chloride, the surface of the activated carbon turns silvery white, which proves that the surface of the activated carbon carrier is loaded with metal aluminum atoms. In the preparation of the catalyst, the loading of the catalyst needs to be controlled to ensure the activity and stability of the catalyst. The catalyst loading of the embodiment of the invention is 35 percent, at this time, not only AlCl is ensured 3 The activity of the catalyst can also be made more stable. FIG. 3 shows the catalyst Al-Mn/C after the addition of Mn element in step S1 of the present inventionFrom the SEM images of (a), the addition of manganese element fills up the rugged small holes on the surface of the activated carbon, and a plurality of small white spots appear on the surface of the activated carbon, which further verifies that the successful doping of manganese element and the morphology of the activated carbon are changed.
Example 2: s1, preparation of an Al-Mn/C catalyst: into a three-necked flask was charged 24 g AlCl 3 Dissolving with a small amount of absolute ethanol, adding 68 g active carbon, loading into reflux condenser, and heating and refluxing for 0.5. 0.5 h to obtain AlCl 3 Fully adsorbing the mixture on the surface of active carbon with the loading capacity of 35%, washing the mixture with a small amount of absolute ethyl alcohol for three times, carrying out suction filtration, carrying out air drying, and then mixing a filter cake and manganese chloride according to the mass ratio of 10:1 in a mortar for 30min, and then put into a quartz bottle of 100 ml, and microwaved in a household microwave oven for 100 seconds. And then taking out, activating 3 h in a baking oven at 130 ℃, and then placing the activated carbon and manganese element supported aluminum chloride catalyst Al-Mn/C in a dryer for cooling to obtain the activated carbon and manganese element supported aluminum chloride catalyst Al-Mn/C. In this step AlCl 3 The sublimation point of (2) is 177.8 ℃, the boiling point is 182.7 ℃, and the reaction temperature of the monomer organosilicon prepared by the invention exceeds AlCl 3 The sublimation point of the aluminum chloride is improved by using the high boiling point of the activated carbon and the activated carbon-supported aluminum chloride. And it is found that after the microwave, the aperture of the activated carbon is filled by adding manganese element, the scanning pattern of the catalyst is changed, and the stability of the supported aluminum chloride catalyst is obviously improved.
S2, synthesizing monomer organic silicon: purging a 2000L high-pressure reaction kettle with nitrogen to remove static air, firstly weighing trimethylsilyl diethylamine 130 g, adding the trimethylhydrogen dichlorosilane 80 g, finally weighing the modified catalyst Al-Mn/C7 g prepared in the step S1, pouring the modified catalyst Al-Mn/C7 g into the reaction kettle, quickly sealing the reaction kettle, regulating the reaction temperature to 220 ℃, reacting 2h, removing a heating device, opening kettle cooling water, cooling to 15 ℃, taking out liquid in the kettle, adding the liquid into a three-mouth bottle, fractionating, and collecting fraction trimethylchlorosilane at 55 ℃. In the step, methylsilane diethylamine and methylhydrogen dichlorosilane are adopted as raw materials, trimethylchlorosilane is distilled at 55 ℃ in the distillation process, aluminum chloride is immobilized by added activated carbon, and manganese element is doped to obtain a catalyst Al-Mn/C, so that the conversion rate of the trimethylsilane diethylamine is increased.
S3, modified 107 silicon rubber: weighing 107 silicon rubber, nickel nitrate and hydrogen-containing silicone oil, putting the 107 silicon rubber, nickel catalyst and the hydrogen-containing silicone oil into a beaker with the ice-water bath temperature of 2 ℃, wherein the mass ratio of the 107 silicon rubber to the nickel catalyst to the hydrogen-containing silicone oil is 40:9:13, adopting a multifunctional dispersing machine to mix nano SiO2 with the mixed rubber according to the mass ratio of 1:56 are thoroughly stirred and applied until the resulting composite is well mixed. Transferring to a vacuum drying oven for vacuum treatment at room temperature, transferring to a plate vulcanizing machine at 120 ℃ and 15 MPa, vulcanizing for 14 min, and then mixing the vulcanized product with molybdenum chloride according to the mass ratio of 10:1 into ethanol, the mixture was stirred in an ultrasonic cell for 30 minutes, followed by further stirring with a magnetic stirrer overnight. And washing the silicon rubber with water for several times after drying, and centrifugally drying the silicon rubber at 60 ℃ to obtain the modified 107 silicon rubber. In the step, 107 silicon rubber is chemically named as hydroxyl-terminated polydimethylsiloxane, nickel nitrate is used as a catalyst, the catalyst and cross-linking agent hydrogen-containing silicone oil are added and fully stirred, and then nano SiO is adopted 2 As modified filler, molybdenum element doping is carried out, so that the 107 silicon rubber has excellent high temperature resistance and dielectric property after vulcanization at room temperature, the conductivity of the 107 silicon rubber can be improved by doping nano silicon dioxide, and the silicon-carbon copolymer prepared in the step S4 and the monomer organic silicon synthesized silicon-carbon copolymer prepared in the step S2 are synthesized.
S4, synthesizing a silicon-carbon copolymer: dissolving the monomer organic silicon prepared in the step S2 and the 107 silicon rubber prepared in the step S3 in N, N-Dimethylformamide (DMF), wherein the mass ratio of the monomer organic silicon to the 107 silicon rubber modified in the step S3 to the DMF is 10:9:21, repeatedly freezing and degassing for five times by liquid nitrogen, polymerizing 22 h under the protection of inert gas Ar, transferring into a clean crucible, placing into a tube furnace, calcining for 2 hours under the protection of inert gas Ar at the temperature of 200 ℃, and obtaining the solid silicon-carbon copolymer. The step is a preparation process of the silicon-carbon copolymer, wherein the monomer organic silicon is trimethylchlorosilane, the step S3 is used for preparing the silicon-carbon copolymer by hydrolyzing the modified 107 silicon rubber, the trimethylchlorosilane and the DMF, the doping of the nano silicon dioxide is used for improving the conductivity of the 107 silicon rubber, and the prepared silicon-carbon copolymer is of a three-dimensional porous structure and has wide prospect in the field of application to battery cathode materials.
S5, preparing an electrode plate and assembling a battery: weighing the silicon-carbon copolymer prepared in the step S4: acetylene black: the mass ratio of the binder is 7:2:1, fully grinding and refining the mixture, placing the mixture in a beaker, adding nitrogen methyl pyrrolidone, carrying out electromagnetic stirring for 12 hours, taking a piece of copper foil, scrubbing the copper foil with absolute ethyl alcohol, pouring the prepared slurry on the copper foil, uniformly scraping the copper foil by a scraper, drying the copper foil in a blast drying oven at 60 ℃ for 12 hours, taking the copper foil as a negative electrode material of a lithium ion battery after punching a raw sheet, taking a pure lithium sheet as a positive electrode, assembling the copper foil into a CR2032 button battery in a glove box filled with argon, and measuring the electrochemical performance of the CR2032 button battery.
Comparative example 1: in the step S2, common AlCl is used 3 The procedure of example 2 was repeated except that the catalyst was used instead of the one according to the invention.
Comparative example 2: the procedure of example 2 was repeated except that the manganese element was not doped in step S1.
FIG. 4 shows the effect of example 2, comparative example 1, comparative example 2 on the stability of the methylsilane-based diethylamine reaction at different catalysts. As can be seen from the graph, the conversion rate of the methylsilyl diethylamine in the operation of the Al-Mn/C catalyst in the example 2 and the comparative example 1 is 100% under the condition that other conditions are unchanged, and the catalyst in the comparative example 1 is only used for 4 times in a stable cycle and is reduced from the 5 th time. Comparative example 2 in the absence of doped manganese element, comparative example 2 was found to have a reduced stability compared to the catalyst of example 1. According to the invention, the manganese element is added to fill the cavity of the activated carbon, and the immobilized aluminum chloride catalyst has remarkable stability, probably because the manganese element and the aluminum element have synergistic effect on the activated carbon, and the manganese element fills the cavity of the activated carbon and fully contacts with the surface of the aluminum chloride, so that the unique catalytic activity is shown. Therefore, the catalyst with the manganese element immobilized and filled by the activated carbon is beneficial to improving the stability of the catalyst.
Example 3: s1, preparation of an Al-Mn/C catalyst: in a three-necked flask25 g AlCl 3 Dissolving with a small amount of absolute ethanol, adding 71 g active carbon, loading into reflux condenser, and heating and refluxing for 0.5. 0.5 h to obtain AlCl 3 Fully adsorbing the mixture on the surface of active carbon with the loading capacity of 35%, washing the mixture with a small amount of absolute ethyl alcohol for three times, carrying out suction filtration, carrying out air drying, and then mixing a filter cake and manganese chloride according to the mass ratio of 10:1 in a mortar for 30min, and then put into a quartz bottle of 100 ml, and microwaved in a household microwave oven for 100 seconds. And then taking out, activating 3 h in an oven at 150 ℃, and then placing the activated carbon and manganese element-supported aluminum chloride catalyst Al-Mn/C in a dryer for cooling to obtain the activated carbon and manganese element-supported aluminum chloride catalyst Al-Mn/C. In this step AlCl 3 The sublimation point of (2) is 177.8 ℃, the boiling point is 182.7 ℃, and the reaction temperature of the monomer organosilicon prepared by the invention exceeds AlCl 3 The sublimation point of the aluminum chloride is improved by using the high boiling point of the activated carbon and the activated carbon-supported aluminum chloride. And it is found that after the microwave, the aperture of the activated carbon is filled by adding manganese element, the scanning pattern of the catalyst is changed, and the stability of the supported aluminum chloride catalyst is obviously improved.
S2, synthesizing monomer organic silicon: purging a 2000L high-pressure reaction kettle with nitrogen to remove static air, firstly weighing trimethylsilyl diethylamine 140 g, adding the trimethylhydrogen dichlorosilane 90 g, finally weighing the modified catalyst Al-Mn/C8 g prepared in the step S1, pouring the modified catalyst Al-Mn/C8 g into the reaction kettle, quickly sealing the reaction kettle, regulating the reaction temperature to 260 ℃, reacting 3 h, removing a heating device, opening kettle cooling water, cooling to 20 ℃, taking out the liquid in the kettle, adding the liquid into a three-mouth bottle, fractionating, and collecting fraction trimethylchlorosilane at 55 ℃. In the step, methylsilane diethylamine and methylhydrogen dichlorosilane are adopted as raw materials, trimethylchlorosilane is distilled at 55 ℃ in the distillation process, and the added activated carbon is used for immobilizing aluminum chloride catalyst Al-Mn/C, so that the conversion rate of trimethylsilane diethylamine is increased.
S3, modified 107 silicon rubber: weighing 107 silicon rubber, nickel nitrate and hydrogen-containing silicone oil, putting into a beaker with ice-water bath temperature of 3 ℃, and catalyzing the 107 silicon rubberThe mass ratio of the nickel to the hydrogen-containing silicone oil is 40:9:13, adopting a multifunctional dispersing machine to disperse nano SiO 2 The mass ratio of the rubber to the mixed rubber is 1:56 are thoroughly stirred and applied until the resulting composite is well mixed. Transferring to a vacuum drying oven for vacuum treatment at room temperature, transferring to a plate vulcanizing machine at 120 ℃ and 15 MPa, vulcanizing for 15 min, and then mixing the vulcanized product with molybdenum chloride according to the mass ratio of 10:1 into ethanol, the mixture was stirred in an ultrasonic cell for 30 minutes, followed by further stirring with a magnetic stirrer overnight. And washing the mixture for a plurality of times after drying, and centrifugally drying the mixture at 60 ℃ to obtain the modified 107 silicone rubber. In the step, 107 silicon rubber is chemically named as hydroxyl-terminated polydimethylsiloxane, nickel nitrate is used as a catalyst, the catalyst and cross-linking agent hydrogen-containing silicone oil are added and fully stirred, and then nano SiO is adopted 2 As modified filler, molybdenum element doping is carried out, so that the 107 silicon rubber has excellent high temperature resistance and dielectric property after vulcanization at room temperature, the conductivity of the 107 silicon rubber can be improved by doping nano silicon dioxide, and the silicon-carbon copolymer prepared in the step S4 and the monomer organic silicon synthesized silicon-carbon copolymer prepared in the step S2 are synthesized.
S4, synthesizing a silicon-carbon copolymer: dissolving the monomer organic silicon prepared in the step S2 and the 107 silicon rubber prepared in the step S3 in N, N-Dimethylformamide (DMF), wherein the mass ratio of the monomer organic silicon to the 107 silicon rubber modified in the step S3 to the DMF is 10:9:21, repeatedly freezing and degassing for five times by liquid nitrogen, polymerizing 28 h under the protection of inert gas Ar, transferring into a clean crucible, placing into a tube furnace, calcining for 2 hours under the protection of inert gas Ar at the temperature of 250 ℃, and obtaining the solid silicon-carbon copolymer. The step is a preparation process of the silicon-carbon copolymer, wherein the monomer organic silicon is trimethylchlorosilane, the step S3 is used for preparing the silicon-carbon copolymer by hydrolyzing the modified 107 silicon rubber, the trimethylchlorosilane and the DMF, the doping of the nano silicon dioxide is used for improving the conductivity of the 107 silicon rubber, and the prepared silicon-carbon copolymer is of a three-dimensional porous structure and has wide prospect in the field of application to battery cathode materials.
S5, preparing an electrode plate and assembling a battery: weighing the silicon-carbon copolymer prepared in the step S4: acetylene black: the mass ratio of the binder is 7:2:1, fully grinding and refining the mixture, placing the mixture in a beaker, adding nitrogen methyl pyrrolidone, carrying out electromagnetic stirring for 12 hours, taking a piece of copper foil, scrubbing the copper foil with absolute ethyl alcohol, pouring the prepared slurry on the copper foil, uniformly scraping the copper foil by a scraper, drying the copper foil in a blast drying oven at 60 ℃ for 12 hours, taking the copper foil as a negative electrode material of a lithium ion battery after punching a raw sheet, taking a pure lithium sheet as a positive electrode, assembling the copper foil into a CR2032 button battery in a glove box filled with argon, and measuring the electrochemical performance of the CR2032 button battery.
Comparative example 3: no nano SiO is used in the step S3 2 The procedure of example 3 was repeated except for the modified 107 silicone rubber.
Comparative example 4: the procedure of example 3 was repeated except that the molybdenum element-modified 107 silicone rubber was not doped in step S3.
The method for testing the electrical conductivity of 107 silicon rubber prepared by the invention comprises the steps of firstly placing a prepared 107 silicon rubber sample in an electrothermal vacuum drying oven for pretreatment for 24 hours, taking out the sample, plating an aluminum foil electrode on the sample, and then measuring the 107 silicon rubber sample before and after nano modification by adopting a three-electrode system at 25 ℃, 40 ℃, 55 ℃ and 70 ℃, wherein table 1 shows the electrical conductivity (S/m) of 107 silicon rubber of the same electric field strength at different temperatures in example 3, comparative example 3 and comparative example 4, and the test results are shown in the following table.
TABLE 1
| Project | Example 3 | Comparative example 3 | Comparative example 4 |
| 25℃ | 7.5±0.1×10 -15 | 1.1±0.2×10 -15 | 5.3±0.1×10 -15 |
| 40℃ | 8.6±0.2×10 -15 | 1.9±0.3×10 -15 | 5.7±0.3×10 -15 |
| 55℃ | 1.3±0.1×10 -14 | 2.5±0.3×10 -15 | 6.1±0.2×10 -15 |
| 70℃ | 2.2±0.3×10 -14 | 4.0±0.1×10 -15 | 6.6±0.1×10 -15 |
As can be seen from the table, the electrical conductivity of the silicone rubber of example 3 was higher than that of comparative example 3 and comparative example 4, and the electrical conductivity of the silicone rubber of example 3 was increased with the increase of temperature at different temperatures of 25 ℃, 40 ℃, 55 ℃ and 70 ℃, and the electrical conductivity changes of the silicone rubbers of comparative example 3 and comparative example 4 were not significant. When the temperature is the same, nano SiO 2 The conductivity of the silicon rubber obtained by co-doping with molybdenum element is improved because of nano SiO 2 The nano modified composite material can be used as a semiconductor material, and molybdenum element is combined, and the material can form a conductive network locally due to the synergistic effect of the semiconductor material and the molybdenum element, so that the conductivity of the nano modified composite material is increased. So the modified 107 silicon rubber has conductivity, and the prepared silicon-carbon copolymer can be used as a battery cathode material in the field of battery industry.
Example 4: s1, alPreparation of Mn/C catalyst: into a three-necked flask was charged 33 g AlCl 3 Dissolving with a small amount of absolute ethanol, adding 94 g active carbon, loading into reflux condenser, and heating and refluxing for 0.5. 0.5 h to obtain AlCl 3 Fully adsorbing the mixture on the surface of active carbon with the loading capacity of 35%, washing the mixture with a small amount of absolute ethyl alcohol for three times, carrying out suction filtration, carrying out air drying, and then mixing a filter cake and manganese chloride according to the mass ratio of 10:1 in a mortar for 30min, and then put into a quartz bottle of 100 ml, and microwaved in a household microwave oven for 100 seconds. And then taking out, activating 2h in a baking oven at 140 ℃, and then placing the activated carbon and manganese element supported aluminum chloride catalyst Al-Mn/C in a dryer for cooling to obtain the activated carbon and manganese element supported aluminum chloride catalyst Al-Mn/C. In this step AlCl 3 The sublimation point of (2) is 177.8 ℃, the boiling point is 182.7 ℃, and the reaction temperature of the monomer organosilicon prepared by the invention exceeds AlCl 3 The sublimation point of the aluminum chloride is improved by using the high boiling point of the activated carbon and the activated carbon-supported aluminum chloride. And it is found that after the microwave, the aperture of the activated carbon is filled by adding manganese element, the scanning pattern of the catalyst is changed, and the stability of the supported aluminum chloride catalyst is obviously improved.
S2, synthesizing monomer organic silicon: purging a 2000L high-pressure reaction kettle with nitrogen to remove static air, firstly weighing trimethylsilyl diethylamine 200 g, adding into the reaction kettle, secondly weighing methylhydrogen dichlorosilane 100 g, finally weighing modified catalyst Al-Mn/C10 g prepared in the step S1, pouring into the reaction kettle, rapidly sealing the reaction kettle, regulating the reaction temperature to 300 ℃, reacting 3 h, removing a heating device, opening kettle cooling water, cooling to 25 ℃, taking out liquid in the kettle, adding into a three-mouth bottle for fractionation, and collecting fraction trimethylchlorosilane at 65 ℃. In the step, methylsilane diethylamine and methylhydrogen dichlorosilane are adopted as raw materials, trimethylchlorosilane is distilled at 65 ℃ in the distillation process, aluminum chloride is immobilized by added activated carbon, and manganese element is doped to obtain a catalyst Al-Mn/C, so that the conversion rate of the trimethylsilane diethylamine is increased.
S3, modified 107 silicon rubber: weighing 107 silicon rubber, nickel nitrate,Putting hydrogen-containing silicone oil into a beaker with ice-water bath temperature of 4 ℃, wherein the mass ratio of 107 silicone rubber to catalyst nickel to hydrogen-containing silicone oil is 40:9:13, adopting a multifunctional dispersing machine to disperse nano SiO 2 The mass ratio of the rubber to the mixed rubber is 1:56 are thoroughly stirred and applied until the resulting composite is well mixed. Transferring to a vacuum drying oven for vacuum treatment at room temperature, transferring to a plate vulcanizing machine at 120 ℃ and 15 MPa, vulcanizing for 20 min, and then mixing the vulcanized product with molybdenum chloride according to the mass ratio of 10:1 into ethanol, the mixture was stirred in an ultrasonic cell for 30 minutes, followed by further stirring with a magnetic stirrer overnight. And washing the mixture for a plurality of times after drying, and centrifugally drying the mixture at 60 ℃ to obtain the modified 107 silicone rubber. In the step, 107 silicon rubber is chemically named as hydroxyl-terminated polydimethylsiloxane, nickel nitrate is used as a catalyst, the catalyst and cross-linking agent hydrogen-containing silicone oil are added and fully stirred, and then nano SiO is adopted 2 As modified filler, molybdenum element doping is carried out, so that the 107 silicon rubber has excellent high temperature resistance and dielectric property after vulcanization at room temperature, the conductivity of the 107 silicon rubber can be improved by doping nano silicon dioxide, and the silicon-carbon copolymer prepared in the step S4 and the monomer organic silicon synthesized silicon-carbon copolymer prepared in the step S2 are synthesized.
S4, synthesizing a silicon-carbon copolymer: dissolving the monomer organic silicon prepared in the step S2 and the 107 silicon rubber prepared in the step S3 in N, N-Dimethylformamide (DMF), wherein the mass ratio of the monomer organic silicon to the 107 silicon rubber modified in the step S3 to the DMF is 10:9:21, repeatedly freezing and degassing for five times by liquid nitrogen, polymerizing 30 h under the protection of inert gas Ar, transferring into a clean crucible, placing into a tube furnace, calcining for 2 hours under the protection of inert gas Ar at the temperature of 350 ℃, and obtaining the solid silicon-carbon copolymer. The step is a preparation process of the silicon-carbon copolymer, wherein the monomer organic silicon is trimethylchlorosilane, the step S3 is used for preparing the silicon-carbon copolymer by hydrolyzing the modified 107 silicon rubber, the trimethylchlorosilane and the DMF, the doping of the nano silicon dioxide is used for improving the conductivity of the 107 silicon rubber, and the prepared silicon-carbon copolymer is of a three-dimensional porous structure and has wide prospect in the field of application to battery cathode materials.
S5, preparing an electrode plate and assembling a battery: weighing the silicon-carbon copolymer prepared in the step S4: acetylene black: the mass ratio of the binder is 7:2:1, fully grinding and refining the mixture, placing the mixture in a beaker, adding nitrogen methyl pyrrolidone, carrying out electromagnetic stirring for 12 hours, taking a piece of copper foil, scrubbing the copper foil with absolute ethyl alcohol, pouring the prepared slurry on the copper foil, uniformly scraping the copper foil by a scraper, drying the copper foil in a blast drying oven at 60 ℃ for 12 hours, taking the copper foil as a negative electrode material of a lithium ion battery after punching a raw sheet, taking a pure lithium sheet as a positive electrode, assembling the copper foil into a CR2032 button battery in a glove box filled with argon, and measuring the electrochemical performance of the CR2032 button battery.
Comparative example 4: the procedure of example 4 was repeated except that commercial graphite was used as the negative electrode in place of the silicon carbon copolymer prepared in the present invention in step S5.
Fig. 5 is an SEM image of a silicon carbon copolymer material of example 4 of the present invention. From the figure, the microstructure of the material has a plurality of pore channels, loose and porous, and the pores are favorable for lithium ion intercalation and deintercalation. Fig. 6 is a graph of the cycling performance of the inventive example 4 silicon carbon copolymer assembled lithium battery and the comparative example 4 commercial lithium battery tested on a blue electrical tester. From the graph, it can be seen that the performance of the lithium ion battery of example 4 is 1200 mAhg after the rest of 12h -1 The battery performance of comparative example 4 was 520 mAhg -1 . Therefore, the lithium ion battery of the embodiment 4 is better in performance through comparison, and the silicon-carbon copolymer has popularization and application values in the battery field.
The above embodiments are merely illustrative of the preparation process of the present invention, and not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solution of the present invention should fall within the protection scope defined by the claims of the present invention without departing from the design spirit of the present invention.
Claims (10)
1. A silicon-carbon copolymer and a preparation method thereof are characterized in that: the preparation method comprises the following specific steps:
s1, preparation of an Al-Mn/C catalyst: 23-33 g AlCl is added into a three-necked flask 3 And a small amount of absolute ethyl alcohol to be completely dissolved, and then 65-94 g of active carbon is added into the mixture to be put into a reflux condenser tube for heating reflux for 0.5, h, washing with a small amount of absolute ethyl alcohol for three times, carrying out suction filtration, air-drying, and then mixing a filter cake and manganese chloride according to the mass ratio of 10:1 in the mortar, uniformly mixing the materials, then placing the materials into a quartz bottle of 100 ml, carrying out microwave for 100 seconds in a household microwave oven, then taking out the materials, activating the materials in an oven of 100-150 ℃ for 2-3 hours, and then placing the materials in a dryer for cooling, thus obtaining the catalyst Al-Mn/C of activated carbon and manganese element immobilized aluminum chloride;
s2, synthesizing monomer organic silicon: purging a 2000-L high-pressure reaction kettle with nitrogen to remove static air, firstly weighing 110-200 g of trimethylsilyl diethylamine, adding into the reaction kettle, secondly weighing 70-100 g of monomethyl hydrogen dichlorosilane, finally weighing 6-10 g of modified catalyst Al-Mn/C prepared in the step S1, pouring into the reaction kettle, rapidly sealing the reaction kettle, adjusting the reaction temperature to 200-300 ℃, reacting for 2-3 hours, removing a heating device, opening kettle cooling water, cooling to 10-25 ℃, taking out liquid in the kettle, adding into a three-mouth bottle for fractionation, and collecting fraction trimethylchlorosilane at 50-65 ℃;
s3, modified 107 silicon rubber: weighing 107 silicon rubber, nickel nitrate and hydrogen-containing silicone oil, putting the 107 silicon rubber, nickel nitrate and hydrogen-containing silicone oil into a beaker with the ice-water bath temperature of 0-4 ℃, wherein the mass ratio of the 107 silicon rubber to the catalyst nickel to the hydrogen-containing silicone oil is 40:9:13, adopting a multifunctional dispersing machine to disperse nano SiO 2 The mass ratio of the rubber to the mixed rubber is 1:56, fully stirring until the formed composite material is uniformly mixed, transferring to a vacuum drying oven, performing vacuum treatment at room temperature, transferring to a flat vulcanizing machine at 120 ℃ and 15 MPa, vulcanizing for 10-20 min, and then mixing the vulcanized product with molybdenum chloride according to the mass ratio of 10:1 dispersing into ethanol, stirring the mixture in an ultrasonic pool for 30min, then further stirring for one night by using a magnetic stirrer, washing with water for several times after drying, and centrifugally drying at 60 ℃ to obtain modified 107 silicone rubber;
s4, synthesizing a silicon-carbon copolymer: dissolving the monomer organic silicon prepared in the step S2 and the 107 silicon rubber prepared in the step S3 into N, N-dimethylformamide, wherein the mass ratio of the monomer organic silicon to the 107 silicon rubber modified in the step S3 to DMF is 10:9:21, repeatedly freezing and degassing for five times by liquid nitrogen, polymerizing for 20-30 hours under the protection of inert gas Ar, transferring to a clean crucible, placing into a tubular furnace, calcining for 2 hours under the protection of inert gas Ar at the temperature of 150-350 ℃, and obtaining a solid silicon-carbon copolymer;
s5, preparing an electrode plate and assembling a battery: weighing the silicon-carbon copolymer prepared in the step S4: acetylene black: the mass ratio of the binder is 7:2:1, fully grinding and refining the mixture, placing the mixture in a beaker, adding nitrogen methyl pyrrolidone, carrying out electromagnetic stirring on the mixture 12, h, taking a piece of copper foil, scrubbing the copper foil with absolute ethyl alcohol, pouring the prepared slurry on the copper foil, uniformly scraping the copper foil by a scraper, drying the copper foil in a blast drying oven at 60 ℃ for 12h, taking the copper foil as a negative electrode material of a lithium ion battery after punching a raw sheet, taking a pure lithium sheet as a positive electrode, assembling the copper foil into a CR2032 button battery in a glove box filled with argon, and measuring the electrochemical performance of the copper foil.
2. The silicon-carbon copolymer and the preparation method thereof according to claim 1, wherein: in the step S1, 100 g AlCl is added into a three-necked flask 3 。
3. A silicon-carbon copolymer and a method for producing the same according to claim 1 or 3, characterized in that: 40 g active carbon is added in the step S1.
4. A silicon-carbon copolymer and a preparation method thereof as claimed in claim 3, wherein: in the step S2, the trimethylsilyl diethylamine 110 and g are weighed and added into a reaction kettle.
5. A silicon-carbon copolymer and a method for producing the same according to claim 1 or 4, characterized in that: in the step S2, methylhydrogen dichlorosilane 70 and g are weighed.
6. The silicon-carbon copolymer and the preparation method thereof according to claim 5, wherein: the temperature of the ice water bath in the step S3 is 2 ℃.
7. A silicon-carbon copolymer and a method for producing the same according to claim 1 or 6, characterized in that: and in the step S3, the vulcanizing time is 10 min.
8. The silicon-carbon copolymer and the preparation method thereof according to claim 7, wherein: the step S4 is to polymerize 20 h under the protection of inert gas Ar.
9. The silicon-carbon copolymer prepared by the preparation method of any one of claims 1 to 8.
10. Use of the silicon-carbon copolymer as defined in claim 9 in a negative electrode material of a battery.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103214675A (en) * | 2013-05-03 | 2013-07-24 | 中国科学院化学研究所 | Poly(methylsilane-carbosilane) and preparation method thereof |
| CN106964337A (en) * | 2016-01-14 | 2017-07-21 | 万华化学集团股份有限公司 | A kind of preparation method of epoxidation catalyst and the epoxidation catalyst prepared and its application |
| CN107474821A (en) * | 2016-06-07 | 2017-12-15 | 上海交通大学 | A kind of Silica-coated quantum dot and preparation method thereof |
| CN110183668A (en) * | 2019-06-17 | 2019-08-30 | 凌至新材料(泸州)有限公司 | A kind of silicon-carbon copolymer and its preparation method and application |
| CN112759953A (en) * | 2020-12-30 | 2021-05-07 | 浙江凌志新材料有限公司 | Single-component silicon-carbon modified real stone paint and preparation method thereof |
| CN112919480A (en) * | 2021-02-01 | 2021-06-08 | 中国石油天然气股份有限公司 | Dihydroxy silica gel, preparation method thereof and detection system for concentration of functional polymer in produced liquid |
| CN116082384A (en) * | 2023-04-12 | 2023-05-09 | 南京首开化工有限公司 | Process for synthesizing trimethylchlorosilane by utilizing organosilicon low-boiling byproducts |
-
2023
- 2023-09-08 CN CN202311158773.8A patent/CN117186416A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103214675A (en) * | 2013-05-03 | 2013-07-24 | 中国科学院化学研究所 | Poly(methylsilane-carbosilane) and preparation method thereof |
| CN106964337A (en) * | 2016-01-14 | 2017-07-21 | 万华化学集团股份有限公司 | A kind of preparation method of epoxidation catalyst and the epoxidation catalyst prepared and its application |
| CN107474821A (en) * | 2016-06-07 | 2017-12-15 | 上海交通大学 | A kind of Silica-coated quantum dot and preparation method thereof |
| CN110183668A (en) * | 2019-06-17 | 2019-08-30 | 凌至新材料(泸州)有限公司 | A kind of silicon-carbon copolymer and its preparation method and application |
| CN112759953A (en) * | 2020-12-30 | 2021-05-07 | 浙江凌志新材料有限公司 | Single-component silicon-carbon modified real stone paint and preparation method thereof |
| CN112919480A (en) * | 2021-02-01 | 2021-06-08 | 中国石油天然气股份有限公司 | Dihydroxy silica gel, preparation method thereof and detection system for concentration of functional polymer in produced liquid |
| CN116082384A (en) * | 2023-04-12 | 2023-05-09 | 南京首开化工有限公司 | Process for synthesizing trimethylchlorosilane by utilizing organosilicon low-boiling byproducts |
Non-Patent Citations (10)
| Title |
|---|
| 兰州化学工业公司编: "《合成橡胶工业知识》", 30 September 1972, 燃料化学工业出版社, pages: 85 - 86 * |
| 吕选忠等: "《元素生物学》", 31 January 2011, 中国科学技术大学出版社, pages: 468 - 470 * |
| 姜节俭: "《有机绝缘材料》", 31 May 1961, 北京科学教育编辑室, pages: 91 - 93 * |
| 晨光化工研究院 有机硅编写组: "《有机硅单体及聚合物》", 31 December 1986, 化学工业出版社, pages: 128 - 130 * |
| 李强等: "《新能源系统储能原理与技术》", 31 December 2021, 机械工业出版社, pages: 4 - 7 * |
| 杰西·鲁兹洛等: "《半导体工程导论》", 31 January 2022, 机械工业出版社, pages: 22 * |
| 潘小勇等: "《新能源技术》", 30 November 2019, 江西高校出版社, pages: 235 - 237 * |
| 童身毅等: "《涂料树脂合成与配方原理》", 30 November 1990, 华中理工大学出版社, pages: 128 * |
| 董永春: "《纺织助剂化学与应用》", 31 July 2007, 中国纺织出版社, pages: 103 * |
| 魏文德: "《有机化工原料大全》", 31 March 1994, 《有机化工原料大全》, pages: 394 * |
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