CN114284479A - Preparation method of novel carbon-silicon negative electrode material - Google Patents
Preparation method of novel carbon-silicon negative electrode material Download PDFInfo
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- CN114284479A CN114284479A CN202111579750.5A CN202111579750A CN114284479A CN 114284479 A CN114284479 A CN 114284479A CN 202111579750 A CN202111579750 A CN 202111579750A CN 114284479 A CN114284479 A CN 114284479A
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- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000009987 spinning Methods 0.000 claims abstract description 46
- 239000000243 solution Substances 0.000 claims abstract description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 11
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 11
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 10
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 9
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 7
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- 239000004094 surface-active agent Substances 0.000 claims abstract description 7
- 238000005245 sintering Methods 0.000 claims abstract description 6
- 239000012266 salt solution Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000010405 anode material Substances 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical group [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 6
- SZEMGTQCPRNXEG-UHFFFAOYSA-M trimethyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C SZEMGTQCPRNXEG-UHFFFAOYSA-M 0.000 claims description 6
- XQSBLCWFZRTIEO-UHFFFAOYSA-N hexadecan-1-amine;hydrobromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[NH3+] XQSBLCWFZRTIEO-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 4
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 4
- 239000003822 epoxy resin Substances 0.000 claims description 4
- 229920000647 polyepoxide Polymers 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229910000077 silane Inorganic materials 0.000 claims description 4
- 239000004246 zinc acetate Substances 0.000 claims description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 3
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 claims description 3
- NLSFWPFWEPGCJJ-UHFFFAOYSA-N 2-methylprop-2-enoyloxysilicon Chemical compound CC(=C)C(=O)O[Si] NLSFWPFWEPGCJJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- NOKSMMGULAYSTD-UHFFFAOYSA-N [SiH4].N=C=O Chemical compound [SiH4].N=C=O NOKSMMGULAYSTD-UHFFFAOYSA-N 0.000 claims description 2
- 229960000583 acetic acid Drugs 0.000 claims description 2
- 239000012362 glacial acetic acid Substances 0.000 claims description 2
- IYMSIPPWHNIMGE-UHFFFAOYSA-N silylurea Chemical compound NC(=O)N[SiH3] IYMSIPPWHNIMGE-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 229910052717 sulfur Inorganic materials 0.000 claims 1
- 239000011593 sulfur Substances 0.000 claims 1
- 239000010406 cathode material Substances 0.000 abstract description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 11
- 229910052710 silicon Inorganic materials 0.000 description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 10
- 239000010703 silicon Substances 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- 230000005684 electric field Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000011149 active material Substances 0.000 description 6
- 239000013543 active substance Substances 0.000 description 6
- 239000012300 argon atmosphere Substances 0.000 description 6
- 239000012530 fluid Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000002121 nanofiber Substances 0.000 description 5
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 229910052814 silicon oxide Inorganic materials 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 230000002427 irreversible effect Effects 0.000 description 3
- 239000002210 silicon-based material Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 2
- 229910052912 lithium silicate Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000011856 silicon-based particle Substances 0.000 description 2
- -1 sulfenyl silane Chemical compound 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- BUZRAOJSFRKWPD-UHFFFAOYSA-N isocyanatosilane Chemical compound [SiH3]N=C=O BUZRAOJSFRKWPD-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011533 mixed conductor Substances 0.000 description 1
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Abstract
The invention relates to the technical field of cathode materials, and provides a preparation method of a novel carbon-silicon cathode material, which comprises the following steps: s1, mixing and stirring a silane coupling agent, a lithium salt, a carbon source, a surfactant, polyacrylonitrile and a solvent to prepare an inner shaft spinning solution; s2, stirring the metal salt solution and polyvinylpyrrolidone to prepare an outer shaft spinning solution; s3, spinning the inner shaft spinning solution and the outer shaft spinning solution to prepare a precursor; and S4, sintering the precursor in an inert atmosphere or a reducing atmosphere to form the carbon-silicon negative electrode material. Through above-mentioned technical scheme, the problem that charge-discharge efficiency is not high among the prior art, and the cycle performance is relatively poor has been solved.
Description
Technical Field
The invention relates to the technical field of cathode materials, in particular to a preparation method of a novel carbon-silicon cathode material.
Background
With the continuous improvement of the requirements of new energy automobiles on the endurance mileage in practical application, the related materials of the power battery are also developed towards the direction of providing higher energy density. The graphite cathode of the traditional lithium ion battery can not meet the existing requirements, and the high-energy-density cathode material becomes a new focus for research pursuit.
The silicon-based material negative electrode is the most preferred choice for improving the negative electrode of battery enterprises and lithium battery materials due to the abundant reserve and the ultrahigh theoretical specific capacity (3840mAh/g), and is one of the most potential next-generation lithium ion battery negative electrode materials. However, the silicon material has a significant disadvantage as a battery negative electrode material: firstly, the silicon volume expansion is caused to be 100-300% in the charging and discharging process, the SEI film is continuously damaged by the huge volume effect, the capacity of the lithium ion battery is continuously reduced, the cycle attenuation is serious, and the service life is reduced; secondly, the silicon is a semiconductor, the conductivity of the silicon is much lower than that of graphite, the irreversible degree in the lithium ion deintercalation process is large, the first coulombic efficiency is further reduced, and the silicon-based material forms Li after lithium intercalation22Si5The alloy phase has serious volume expansion (up to 300 percent) in the process of lithium removal/insertion, is easy to cause cracks and even pulverization of active substances, damages the electrical contact between the active substances and the current collector, and greatly shortens the cycle life. Silicon oxide shows a small volume change during cycling compared to elemental silicon, and byproducts such as lithium oxide and lithium silicate generated in situ during the first lithiation can buffer the volume change and improve cycling stability. However, SiOxThe SiO of the base cathode material can irreversibly consume Li in the first circulation+Generation of Li2O and lithium silicate, resulting in a relatively low initial coulombic efficiency (first coulombic efficiency) for silicon oxides.
The carbonaceous negative electrode material has small volume change in the charge-discharge process and better circulation stability, and is a mixed conductor of ions and electrons; in addition, silicon and carbon have similar chemical properties and are tightly bound, so carbon is often used as the first substrate for the recombination with silicon. In the Si/C composite system, Si particles are used as active substances to provide lithium storage capacity; the C can buffer the volume change of the silicon cathode in the charging and discharging process, improve the conductivity of the Si material and avoid the agglomeration of Si particles in the charging and discharging cycle. Therefore, the Si/C composite material integrates the advantages of the Si/C composite material and has high specific capacity and long cycle life, and is expected to replace graphite to become a new generation of lithium ion battery cathode material. At present, silicon powder and a solid carbon source are generally added into a mixer to be mixed, a mixture containing a coating layer is roasted in an inert atmosphere to obtain a carbon-coated silicon-based composite material, and the carbon-coated silicon-based composite material is mixed with a graphite material to obtain a silicon-carbon negative electrode material.
Disclosure of Invention
The invention provides a preparation method of a novel carbon-silicon anode material, which solves the problems in the related art.
The technical scheme of the invention is as follows:
a preparation method of a novel carbon-silicon anode material comprises the following steps:
s1, mixing and stirring a silane coupling agent, a lithium salt, a carbon source, a surfactant, polyacrylonitrile and a solvent to prepare an inner shaft spinning solution;
s2, stirring the metal salt solution and polyvinylpyrrolidone to prepare an outer shaft spinning solution;
s3, spinning the inner shaft spinning solution and the outer shaft spinning solution to prepare a precursor;
and S4, sintering the precursor in an inert atmosphere or a reducing atmosphere to form the carbon-silicon negative electrode material.
As a further technical scheme, the silane coupling agent is one or more of aminosilane, epoxy silane, sulfenyl silane, methacryloxy silane, vinyl silane, ureido silane, isocyanate silane, tetraethoxysilane and vinyl triethoxysilane.
According to a further technical scheme, the lithium salt is lithium acetate and/or lithium hydroxide, and the organic carbon source is one or more of polyethylene glycol, phenolic resin and epoxy resin.
As a further technical scheme, the surfactant is one or more of cetyl ammonium bromide, octadecyl trimethyl ammonium bromide and stearyl trimethyl ammonium bromide.
As a further technical scheme, the solvent in the step S1 is one or more of water, dimethylformamide, isopropanol, glacial acetic acid and absolute ethyl alcohol. As a further technical scheme, in the step S1, the mass-to-volume ratio of the silane coupling agent, the lithium salt, the carbon source, the surfactant, the polyacrylonitrile and the solvent is (5-20 ml): (0, l-1 g): (0, l-1 g): (0, l-1 g): (0, l-1 g): (100 ml-500 ml).
As a further technical solution, the solvent used in the metal salt solution in the step S2 is one of water, isopropyl alcohol, and alcohol.
As a further technical solution, in the step S2, the metal salt is one of aluminum isopropoxide, butyl titanate and zinc acetate.
As a further technical scheme, in the step S2, the mass volume ratio of the metal salt to the solvent to the polyvinylpyrrolidone is (5-20 ml): 100-500 ml): 0.5-2 g.
As a further technical scheme, in the step S4, the sintering temperature is 600-900 ℃, and the time is 60-180 min.
In a further aspect, in step S3, the spinning is performed under an applied electric field of 10 to 50 kv.
The invention has the beneficial effects that:
1. based on the characteristic that nano-fiber has rapid electron and ion transmission, the invention designs and synthesizes SiO with a novel structurex/C@MOy(M ═ Ti, Si, Al) coaxial nanofiber lithium ion battery negative electrode material. SiO 2xNanofibers significantly increase Li by reducing ion diffusion paths+The diffusion rate of (c); the carbon nano-fiber can obviously improve the electronic conductivity of the material and provide a buffer space for the volume expansion in the charge and discharge process of the battery; the excellent mechanical property of the metal oxide shell can inhibit the Li-ion-induced active material+The material is dropped or pulverized due to the insertion/desorption, and the cycle performance of the active material is improved; the addition of the lithium salt can improve the first charge-discharge efficiency of the active material. Transition metal doping can promote irreversible Li2And O is decomposed, so that the first charge-discharge efficiency of the active material is improved. The advantages mentioned above are combinedWill make SiOxthe/C @ MOy (M ═ Ti, Si and Al) coaxial nanofiber lithium ion battery cathode material has the characteristics of good electrochemical performance, stable structure and the like.
2. In the invention, SiO in core-shell structurexthe/C and metal oxide coating layers can effectively buffer the volume expansion of the active substance in the charging and discharging processes, and meanwhile, the carbon shell layer with excellent mechanical property can inhibit the falling of the active substance, so that the cycle performance of the material is greatly improved.
3. Nanofiber material Li+Short diffusion path, large specific surface area and large porosity, and can effectively promote Li+The rapid intercalation/deintercalation, the provision of sufficient transport channels for electrolyte ions, the introduction of more electrolyte ions to participate in electrochemical reactions, and the effective exertion of the electrochemical properties of the active substance.
4. Addition of lithium salt capable of transition metal doping capable of promoting irreversible Li2And O is decomposed, so that the first charge-discharge efficiency of the active material is improved, and the falling of the active material caused by volume expansion is relieved.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
FIG. 1 shows the specific charge capacity of example 2 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any inventive step, are intended to be within the scope of the present invention.
Example 1
(1) 10ml of vinyltriethoxysilane, 0.2g of lithium acetate, 0.2g of polyethylene glycol, 0.3g of cetylammonium bromide and 0.5g of polyacrylonitrile were dissolved in 150ml of isopropanol and stirred to form an inner-shaft spinning solution.
(2) 10ml of butyl titanate is dissolved in 200ml of alcohol, 0.5g of polyvinylpyrrolidone polymer matrix is added, and the mixture is stirred to form the outer spindle spinning solution.
(3) Spinning the solution under the condition of an external electric field of 15 kv; the spinning conditions were: the spinning distance is 15cm, and the flow rate of the core liquid is 0.25 mm/min; the flow rate of the sheath fluid was 0.25 mm/min.
(4) And (3) transferring the precursor into an argon atmosphere, and carrying out heat treatment at 900 ℃ for 60min to form the carbon-silicon negative electrode material.
Example 2
(1) 5ml of aminosilane, 0.5g of lithium hydroxide, 0.4g of epoxy resin, 0.2g of stearyltrimethylammonium bromide and 1.0g of polyacrylonitrile were dissolved in 200ml of isopropyl alcohol and stirred to form an inner-core spinning solution.
(2) 20ml of aluminum isopropoxide was dissolved in 500ml of alcohol, 2.0g of polyvinylpyrrolidone polymer matrix was added, and stirring was performed to form an outer axial spinning solution.
(3) Spinning the solution under the condition of an external electric field of 15 kv; the spinning conditions were: the spinning distance is 10cm, and the flow rate of the core liquid is 0.20 mm/min; the flow rate of the sheath fluid was 0.20 mm/min.
(4) And (3) transferring the precursor into an argon atmosphere, and carrying out heat treatment at 600 ℃ for 180min to form the carbon-silicon negative electrode material.
Example 3
(1) 15ml of ethyl orthosilicate, 0.8g of lithium acetate, 0.2g of phenolic resin, 0.6g of octadecyl trimethyl ammonium bromide and 0.3g of polyacrylonitrile are dissolved in 300ml of alcohol and stirred to form the inner-shaft spinning solution.
(2) 5ml of zinc acetate is dissolved in 250ml of alcohol, 1.5g of polyvinylpyrrolidone polymer matrix is added, and the mixture is stirred to form the outer shaft spinning solution.
(3) Spinning the solution under the condition of an external electric field of 10 kv; the spinning conditions were: the spinning distance is 20cm, and the flow rate of the core liquid is 0.10 mm/min; the flow rate of the sheath fluid was 0.10 mm/min.
(4) And (3) moving the obtained precursor into an argon atmosphere, and carrying out heat treatment at 800 ℃ for 120min to form the carbon-silicon negative electrode material.
Example 4
(1) 8.0ml of isocyanatosilane, 0.2g of lithium acetate, 0.5g of epoxy resin, 0.3g of cetylammonium bromide and 0.1g of polyacrylonitrile were dissolved in 100ml of isopropanol and stirred to form an inner-core spinning solution.
(2) 5ml of aluminum isopropoxide is dissolved in 100ml of alcohol, 0.5g of polyvinylpyrrolidone polymer matrix is added, and stirring is carried out to form the outer spindle spinning solution.
(3) Spinning the solution under the condition of an external electric field of 50 kv; the spinning conditions were: the spinning distance is 10cm, and the flow rate of the core liquid is 0.20 mm/min; the flow rate of the sheath fluid was 0.20 mm/min.
(4) And (3) transferring the precursor into an argon atmosphere, and carrying out heat treatment at 700 ℃ for 60min to form the carbon-silicon negative electrode material.
Example 5
(1) 5ml of vinylsilane, 0.1g of lithium acetate, 0.1g of polyethylene glycol, 1.0g of cetylammonium bromide and 1.0g of polyacrylonitrile were dissolved in 300ml of water and stirred to form an inner-shaft spinning solution.
(2) 20ml of zinc acetate is dissolved in 500ml of alcohol, 2.0g of polyvinylpyrrolidone polymer matrix is added, and the mixture is stirred to form the outer spindle spinning solution.
(3) Spinning the solution under the condition of 30kv external electric field; the spinning conditions were: the spinning distance is 10cm, and the flow rate of the core liquid is 0.15 mm/min; the flow rate of the sheath fluid was 0.15 mm/min.
(4) And (3) moving the obtained precursor into an argon atmosphere, and carrying out heat treatment at 900 ℃ for 120min to form the carbon-silicon negative electrode material.
Control group
(1) 10ml of vinyltriethoxysilane was dissolved in 150ml of isopropanol and stirred to form an inner-core spinning solution.
(2) 0.5g of polyvinylpyrrolidone polymer matrix was dissolved in 200ml of alcohol and stirred to form an outer axial spinning solution.
(3) Spinning the solution under the condition of an external electric field of 15 kv; the spinning conditions were: the spinning distance is 15cm, and the flow rate of the core liquid is 0.25 mm/min; the flow rate of the sheath fluid was 0.25 mm/min.
(4) And (3) transferring the precursor into an argon atmosphere, and carrying out heat treatment at 900 ℃ for 60min to form the carbon-silicon negative electrode material.
Examples of the experiments
The silicon-carbon negative electrode materials obtained in examples 1-5 and the control group were assembled into a lithium ion battery, a metal lithium plate was used as a counter electrode, a polypropylene porous membrane Celgard2400 was used as a separator, and 1mol/L LiPF was used6The mixed solution of Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC) and dimethyl carbonate (DMC) (EC: EMC: DMC volume ratio is 1: 1: 1) is used as electrolyte, a button cell (CR2032) is assembled in an argon glove box, and the charge and discharge test is carried out on a Xinwei CT-4008 tester after the mixture is kept still for 24 hours. The results are shown in Table 1.
TABLE 1 comparison of the Performance of examples 1-5 with that of the control
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a novel carbon-silicon anode material is characterized by comprising the following steps:
s1, mixing and stirring a silane coupling agent, a lithium salt, a carbon source, a surfactant, polyacrylonitrile and a solvent to prepare an inner shaft spinning solution;
s2, stirring the metal salt solution and polyvinylpyrrolidone to prepare an outer shaft spinning solution;
s3, spinning the inner shaft spinning solution and the outer shaft spinning solution to prepare a precursor;
and S4, sintering the precursor in an inert atmosphere or a reducing atmosphere to form the carbon-silicon negative electrode material.
2. The method for preparing a novel carbon-silicon anode material as claimed in claim 1, wherein the silane coupling agent is one or more of aminosilane, epoxy silane, sulfur-based silane, methacryloxy silane, vinyl silane, ureido silane, isocyanate silane and tetraethoxysilane.
3. The method for preparing a novel carbon-silicon anode material as claimed in claim 1, wherein the lithium salt is lithium acetate and/or lithium hydroxide, and the organic carbon source is one or more of polyethylene glycol, phenolic resin and epoxy resin.
4. The method for preparing a novel carbon-silicon anode material as claimed in claim 1, wherein the surfactant is one or more of cetyl ammonium bromide, stearyl trimethyl ammonium bromide and stearyl trimethyl ammonium bromide.
5. The method for preparing a novel carbon-silicon anode material according to claim 1, wherein the solvent in step S1 is one or more of water, dimethylformamide, isopropanol, glacial acetic acid and absolute ethyl alcohol.
6. The preparation method of the novel carbon-silicon anode material as claimed in claim 1, wherein the mass-to-volume ratio of the silane coupling agent, the lithium salt, the carbon source, the surfactant, the polyacrylonitrile and the solvent in the step S1 is (5-20 ml): (0, l-1 g): (0, l-1 g): (0, l-1 g): (0, l-1 g): (100 ml-500 ml).
7. The method for preparing a novel carbon-silicon anode material according to claim 1, wherein the solvent used in the metal salt solution in step S2 is one of water, isopropanol and alcohol.
8. The method as claimed in claim 1, wherein in step S2, the metal salt is one of aluminum isopropoxide, butyl titanate and zinc acetate.
9. The method as claimed in claim 7, wherein in step S2, the mass/volume ratio of the metal salt to the solvent and polyvinylpyrrolidone is (5-20 ml): (100-500 ml): (0.5-2 g).
10. The method for preparing a novel carbon-silicon anode material as claimed in claim 1, wherein in step S4, the sintering temperature is 600-900 ℃ and the sintering time is 60-180 min.
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