CN117486196A - Porous carbon precursor material, silicon carbon material and preparation method - Google Patents
Porous carbon precursor material, silicon carbon material and preparation method Download PDFInfo
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- CN117486196A CN117486196A CN202311444781.9A CN202311444781A CN117486196A CN 117486196 A CN117486196 A CN 117486196A CN 202311444781 A CN202311444781 A CN 202311444781A CN 117486196 A CN117486196 A CN 117486196A
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- 239000000463 material Substances 0.000 title claims abstract description 52
- 239000007833 carbon precursor Substances 0.000 title claims abstract description 50
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 32
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 title claims description 24
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 52
- 239000007787 solid Substances 0.000 claims abstract description 52
- 239000002994 raw material Substances 0.000 claims abstract description 49
- 239000011148 porous material Substances 0.000 claims abstract description 37
- 238000001914 filtration Methods 0.000 claims abstract description 26
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims abstract description 23
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000005530 etching Methods 0.000 claims abstract description 21
- 238000004132 cross linking Methods 0.000 claims abstract description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 16
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims abstract description 15
- 238000010000 carbonizing Methods 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 13
- 239000011261 inert gas Substances 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 9
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 4
- 230000001376 precipitating effect Effects 0.000 claims abstract description 4
- 238000002791 soaking Methods 0.000 claims abstract description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 22
- 229910001416 lithium ion Inorganic materials 0.000 claims description 22
- -1 acrylic ester Chemical class 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 238000003763 carbonization Methods 0.000 claims description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 239000010405 anode material Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000007773 negative electrode material Substances 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000003921 oil Substances 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 3
- 125000004428 fluoroalkoxy group Chemical group 0.000 claims description 3
- 125000001188 haloalkyl group Chemical group 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000004417 unsaturated alkyl group Chemical group 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 229920000642 polymer Polymers 0.000 abstract description 30
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 abstract description 3
- 238000010526 radical polymerization reaction Methods 0.000 abstract description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 abstract description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 239000012300 argon atmosphere Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 238000001035 drying Methods 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- 239000012299 nitrogen atmosphere Substances 0.000 description 11
- 230000000379 polymerizing effect Effects 0.000 description 11
- 238000005406 washing Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010406 cathode material Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 5
- 238000010298 pulverizing process Methods 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000011856 silicon-based particle Substances 0.000 description 2
- 239000013590 bulk material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
- C01B33/021—Preparation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides a preparation method of a porous carbon precursor material and the porous carbon precursor material, wherein the preparation method comprises the following steps: s1, mixing a first raw material, a second raw material and a third raw material in a first inert gas atmosphere, and performing polymerization crosslinking to obtain a polymerization crosslinking solid; the first raw material is polyacrylate POSS, the second raw material is acrylate monomer, and the chemical formula of the second raw material is; the third raw material is azobisisobutyronitrile AIBN; s2, carbonizing the polymerized and crosslinked solidObtaining an intermediate; s3, placing the intermediate in hydrofluoric acid solution, stirring and soaking, etching silicon oxide components of the intermediate, precipitating, and filtering to obtain a porous carbon precursor material; the Gu Ang POSS is taken as a crosslinking point of the polymer, gelled with methacrylate monomers through free radical polymerization, carbonized at high temperature and removed of SiO through HF etching x A porous carbon material having a uniform pore size can be obtained.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a preparation method of a porous carbon precursor material, a silicon-carbon material prepared by the precursor material, a lithium ion battery anode material containing the silicon-carbon material and a lithium ion battery.
Background
Carbon materials have the properties of high temperature resistance, stable chemical properties and conductivity, and are widely paid attention to as novel industrial materials. The porous carbon material has large specific surface area, developed pore structure, adjustable pore structure, strong conductivity and stable physicochemical property in the charge and discharge process, and can be used as an electrode material of a lithium ion battery. Porous carbon materials can be classified into micropores, mesopores, and macropores according to the diameter size of the pores.
Silicon can be alloyed with lithium, and the theoretical gram capacity of the silicon can reach 4200mAh/g, so that the silicon is considered as a lithium ion battery cathode material with great potential. However, silicon and lithium undergo a large volume expansion after being combined during the charging of the lithium ion battery, and the volume collapses during the discharging, and thus, serious pulverization of silicon occurs during the cyclic charging and discharging, resulting in a drastic deterioration of the electrochemical performance of the lithium ion battery. To solve the problem of expansion and pulverization of silicon, at present, a relatively effective strategy is to combine porous carbon with silicon, nano-disperse silicon particles in a carbon skeleton, and restrict the expansion of the silicon particles by utilizing the porosity of the carbon skeleton, so that the pulverization phenomenon is reduced, and the electrochemical performance of the lithium ion battery is improved. So the porous carbon skeleton is used as a precursor for preparing the silicon-carbon material, and the structure and the preparation of the porous carbon skeleton become very critical.
At present, the porous carbon skeleton of the precursor prepared by a plurality of methods has larger pore diameter and different pore size, and the consistency of the physical and chemical properties is required to be further improved; and the large pore diameter of the silicon-carbon material enables the size of the formed silicon crystal particles to be larger when the silicon-carbon material is prepared, so that the stress is larger when the silicon-carbon material expands, and the probability of pulverization is higher.
Disclosure of Invention
Aiming at the technical problems, the invention provides a preparation method of a porous carbon precursor material with regular nano pore size, and provides a novel silicon carbon material prepared from the porous carbon precursor material and a lithium ion battery anode material; .
The invention provides a preparation method of a porous carbon precursor material, which comprises the following steps:
s1, mixing a first raw material, a second raw material and a third raw material in a first inert gas atmosphere, and performing polymerization crosslinking to obtain a polymerization crosslinking solid;
the first raw material is polyacrylate POSS, and the chemical formula of the first raw material is as follows:
wherein (1)>
The second raw material is an acrylic ester monomer, and the chemical formula of the second raw material is
The third raw material is azobisisobutyronitrile AIBN;
the molar ratio of the first raw material to the second raw material is (1:20) - (1:4000);
s2, carbonizing the polymerized crosslinked solid in a second inert gas atmosphere to obtain an intermediate;
and S3, placing the intermediate in hydrofluoric acid solution, stirring and soaking, etching the silicon oxide component of the intermediate, precipitating and filtering to obtain the porous carbon precursor material.
Preferably, said R 1 The radicals being selected from H, - (CH) 2 ) n CH 3 N is selected from any integer between 0 and 5; r is R 2 The radicals being selected from H, - (CH) 2 ) n CH 3 N is selected from any integer between 0 and 5; r is R 3 Selected from H, halogen, hydroxy, cyanoAny one of a sulfonyl group, a fluorosulfonyl group, a sulfonic acid group, a fluorosulfonyl group, a saturated or unsaturated alkyl group of 1 to 10 carbon atoms, a saturated or unsaturated haloalkyl group of 1 to 10 carbon atoms, an alkoxy group of 1 to 10 carbon atoms, or a fluoroalkoxy group of 1 to 10 carbon atoms.
Preferably, the molar ratio of the first raw material to the second raw material is (1:100) to (1:3000); further preferably, the molar ratio of the first raw material to the second raw material is (1:500) to (1:1500).
Preferably, the polymerization crosslinking is carried out under the oil bath condition of 60-70 ℃, and the first inert gas is nitrogen.
Preferably, the second inert gas is argon, the carbonization temperature ranges from 600 ℃ to 1200 ℃, and the carbonization time ranges from 2 hours to 8 hours.
Preferably, the concentration of the hydrofluoric acid solution is 0.5M-1.5M; the pore size of the porous carbon precursor material is less than 1nm.
The invention provides a porous carbon precursor material, which is prepared by the preparation method.
The invention also provides a silicon-carbon material which is prepared from the porous carbon precursor material.
The invention also provides a lithium ion battery anode material, which comprises a silicon-carbon material, wherein the silicon-carbon material is the silicon-carbon material.
The invention also provides a lithium ion battery, which comprises an anode, a cathode, electrolyte and a diaphragm, wherein the cathode comprises a cathode material, and the cathode material is the cathode material of the lithium ion battery.
The preparation method of the porous carbon precursor material of the invention uses cage-shaped polyhedral oligomeric silsesquioxane (polyhedral oligomeric silsesquioxanes, POSS) as a cross-linking point of a polymer and methacrylate monomers to carry out gelation through free radical polymerization, then carries out high-temperature carbonization, and further carries out HF etching to remove SiO x A porous carbon precursor with uniform pore size can be obtainedA bulk material; according to the preparation method, the pores are derived from the pore diameters remained after the POSS is etched, and the pore diameters of the POSS are uniform, so that the pore diameters of the obtained porous carbon precursor material are uniform in size and about 1nm, the pore diameters of the prepared porous carbon precursor material are controllable and regular, and the prepared silicon carbon material has better electrochemical performance as a negative electrode material of a lithium ion battery.
Drawings
FIG. 1 is a schematic diagram of a porous carbon precursor material obtained by etching an intermediate with a hydrofluoric acid solution in an embodiment of the present invention.
Detailed Description
For a better illustration of the invention, reference is made to the following description of the specific embodiments.
The invention provides a preparation method of a porous carbon precursor material, which comprises the following steps:
s1, mixing a first raw material, a second raw material and a third raw material in an inert gas atmosphere, and performing polymerization crosslinking to obtain a polymerization crosslinking solid; specifically, the polymerization crosslinking is carried out under oil bath conditions of 60 to 70 ℃, and more preferably, the polymerization crosslinking is carried out under oil bath conditions of 65 ℃.
The first raw material is polyacrylate POSS, and the chemical formula of the first raw material is as follows:
wherein (1)>
The second raw material is an acrylic ester monomer, and the chemical formula of the second raw material is
The third raw material is azobisisobutyronitrile AIBN;
in a specific embodiment, the molar ratio of the first raw material to the second raw material is (1:20) to (1:4000); further preferably, the molar ratio of the first raw material to the second raw material is (1:100) to (1:3000); further preferably, the molar ratio of the first raw material to the second raw material is (1:500) to (1:1500); the invention creatively discovers that the proportion of POSS molecules and acrylate monomers influences the proportion of POSS molecules in the whole polymer after crosslinking and curing, thereby directly influencing the pore size number in the final porous carbon; when the acrylic ester monomer/acrylic ester POSS (mol/mol) is not less than 20:1, the POSS ratio is not very high, so that the number of pore diameters of the formed porous carbon skeleton is not very large, and meanwhile, the wall thickness of the supported pore diameter is enough, so that the stability of the porous carbon structure is better, and the structure is not easy to collapse; when the ratio of acrylic ester monomer to acrylic ester POSS (mol/mol) is not more than 4000:1, the POSS ratio is not very low, so that the number of pore diameters of the formed porous carbon skeleton is not very small, and the integral performance of the material can be effectively improved.
In a specific embodiment, said R 1 The radicals being selected from H, - (CH) 2 ) n CH 3 N is selected from any integer between 0 and 5; r is R 2 The radicals being selected from H, - (CH) 2 ) n CH 3 N is selected from any integer between 0 and 5; r is R 3 Selected from any one of H, halogen, hydroxyl, cyano, sulfonyl, fluorosulfonyl, sulfonic acid, fluorosulfonyl, saturated or unsaturated alkyl of 1-10 carbon atoms, saturated or unsaturated haloalkyl of 1-10 carbon atoms, alkoxy of 1-10 carbon atoms, or fluoroalkoxy of 1-10 carbon atoms.
S2, carbonizing the polymerized crosslinked solid in a second inert gas atmosphere to obtain an intermediate; specifically, the second inert gas is argon, the carbonization temperature is 600-1200 ℃, and the carbonization time is 2-8 hours; by adopting argon as inert protective gas, an inert environment is provided, and the temperature and time are controlled, so that the solid obtained by polymerization and crosslinking is completely carbonized.
S3, placing the intermediate in hydrofluoric acid solution, stirring and soaking, etching the silicon oxide component of the intermediate, precipitating and filtering to obtain the porous carbon precursor material; specifically, the concentration of the hydrofluoric acid solution is 0.5M-1.5M, and the hydrofluoric acid solution is stirred at the constant temperature of 45 ℃ to enable the hydrofluoric acid solution to fully react and etch silicon oxide components; the purpose of this step is to etch away the carbonized POSS to form a porous, specifically porous carbon precursor material with a pore size of less than 1nm.
The invention provides a porous carbon precursor material, which is prepared by the preparation method.
The invention also provides a silicon-carbon material which is prepared from the porous carbon precursor material.
The invention also provides a lithium ion battery anode material, which comprises a silicon-carbon material, wherein the silicon-carbon material is the silicon-carbon material.
The invention also provides a lithium ion battery, which comprises an anode, a cathode, electrolyte and a diaphragm, wherein the cathode comprises a cathode material, and the cathode material is the cathode material of the lithium ion battery.
The preparation method of the porous carbon precursor material of the invention uses cage-shaped polyhedral oligomeric silsesquioxane (polyhedral oligomeric silsesquioxanes, POSS) as a cross-linking point of a polymer and methacrylate monomers to carry out gelation through free radical polymerization, then carries out high-temperature carbonization, and further carries out HF etching to remove SiO x Porous carbon materials with uniform pore sizes can be obtained; according to the preparation method, the pores are derived from the pore diameters remained after the POSS is etched, and the pore diameters of the POSS are uniform, so that the pore diameters of the obtained porous carbon material are uniform in size and about 1nm, and the pore diameters of the prepared porous carbon precursor material are controllable and regular, so that the prepared silicon carbon material has better electrochemical performance as a negative electrode material of a lithium ion battery.
The invention is further described by the following examples, which are given solely for the purpose of illustration and are not intended to be limiting.
Example 1
Adding MMA monomer and MMA-POSS monomer into a reaction bottle according to the mol ratio of 20:1, adding 0.5% AIBN of the sum of the mol numbers of the MMA monomer and the MMA-POSS monomer, stirring and mixing uniformly under nitrogen atmosphere, polymerizing and curing at the constant temperature of 65 ℃, and drying the obtained solid in an oven after curing is completed. And (3) placing the dried polymer solid in a fixed bed reactor, heating to 1000 ℃ under an argon atmosphere, preserving heat for 6 hours, and carbonizing the obtained polymer solid. And (3) placing the carbonized intermediate in a 1M HF solution to react for 6 hours at 45 ℃, etching the silicon oxide component, filtering, washing with deionized water for three times, and collecting the solid obtained after filtering to obtain the prepared porous carbon precursor material.
Example 2
Adding MMA monomer and MMA-POSS monomer into a reaction bottle according to the mol ratio of 100:1, adding 0.5% AIBN of the sum of the mol numbers of the MMA monomer and the MMA-POSS monomer, stirring and mixing uniformly under nitrogen atmosphere, polymerizing and curing at the constant temperature of 65 ℃, and drying the obtained solid in an oven after curing is completed. And (3) placing the dried polymer solid in a fixed bed reactor, heating to 1000 ℃ under an argon atmosphere, preserving heat for 6 hours, and carbonizing the obtained polymer solid. And (3) placing the carbonized intermediate in a 1M HF solution to react for 6 hours at 45 ℃, etching the silicon oxide component, filtering, washing with deionized water for three times, and collecting the solid obtained after filtering to obtain the prepared porous carbon precursor material.
Example 3
Adding MMA monomer and MMA-POSS monomer into a reaction bottle according to the mol ratio of 500:1, adding 0.5% AIBN of the sum of the mol numbers of the MMA monomer and the MMA-POSS monomer, stirring and mixing uniformly under nitrogen atmosphere, polymerizing and curing at the constant temperature of 65 ℃, and drying the obtained solid in an oven after curing is completed. And (3) placing the dried polymer solid in a fixed bed reactor, heating to 1000 ℃ under an argon atmosphere, preserving heat for 6 hours, and carbonizing the obtained polymer solid. And (3) placing the carbonized intermediate in a 1M HF solution to react for 6 hours at 45 ℃, etching the silicon oxide component, filtering, washing with deionized water for three times, and collecting the solid obtained after filtering to obtain the prepared porous carbon precursor material.
Example 4
Adding MMA monomer and MMA-POSS monomer into a reaction bottle according to the mol ratio of 1000:1, adding 0.5% AIBN of the sum of the mol numbers of the MMA monomer and the MMA-POSS monomer, stirring and mixing uniformly under nitrogen atmosphere, polymerizing and curing at the constant temperature of 65 ℃, and drying the obtained solid in an oven after curing is completed. And (3) placing the dried polymer solid in a fixed bed reactor, heating to 1000 ℃ under an argon atmosphere, preserving heat for 6 hours, and carbonizing the obtained polymer solid. And (3) placing the carbonized intermediate in a 1M HF solution to react for 6 hours at 45 ℃, etching the silicon oxide component, filtering, washing with deionized water for three times, and collecting the solid obtained after filtering to obtain the prepared porous carbon precursor material.
Example 5
Adding MMA monomer and MMA-POSS monomer into a reaction bottle according to the mol ratio of 1500:1, adding 0.5% AIBN of the sum of the mol numbers of the MMA monomer and the MMA-POSS monomer, stirring and mixing uniformly under nitrogen atmosphere, polymerizing and curing at the constant temperature of 65 ℃, and drying the obtained solid in an oven after curing is completed. And (3) placing the dried polymer solid in a fixed bed reactor, heating to 1000 ℃ under an argon atmosphere, preserving heat for 6 hours, and carbonizing the obtained polymer solid. And (3) placing the carbonized intermediate in a 1M HF solution to react for 6 hours at 45 ℃, etching the silicon oxide component, filtering, washing with deionized water for three times, and collecting the solid obtained after filtering to obtain the prepared porous carbon precursor material.
Example 6
Adding MMA monomer and MMA-POSS monomer into a reaction bottle according to the molar ratio of 2000:1, adding O.5% AIBN of the sum of the molar numbers of the MMA monomer and the MMA-POSS monomer, stirring and mixing uniformly under nitrogen atmosphere, polymerizing and curing at the constant temperature of 65 ℃, and drying the obtained solid in an oven after curing is completed. And (3) placing the dried polymer solid in a fixed bed reactor, heating to 1000 ℃ under an argon atmosphere, preserving heat for 6 hours, and carbonizing the obtained polymer solid. And (3) placing the carbonized intermediate in a 1M HF solution to react for 6 hours at 45 ℃, etching the silicon oxide component, filtering, washing with deionized water for three times, and collecting the solid obtained after filtering to obtain the prepared porous carbon precursor material.
Example 7
Adding MMA monomer and MMA-POSS monomer into a reaction bottle according to the mol ratio of 3000:1, adding 0.5% AIBN of the sum of the mol numbers of the MMA monomer and the MMA-POSS monomer, stirring and mixing uniformly under nitrogen atmosphere, polymerizing and curing at the constant temperature of 65 ℃, and drying the obtained solid in an oven after curing is completed. And (3) placing the dried polymer solid in a fixed bed reactor, heating to 1000 ℃ under an argon atmosphere, preserving heat for 6 hours, and carbonizing the obtained polymer solid. And (3) placing the carbonized intermediate in a 1M HF solution to react for 6 hours at 45 ℃, etching the silicon oxide component, filtering, washing with deionized water for three times, and collecting the solid obtained after filtering to obtain the prepared porous carbon precursor material.
Example 8
Adding MMA monomer and MMA-POSS monomer into a reaction bottle according to the mol ratio of 4000:1, adding 0.5% AIBN of the sum of the mol numbers of the MMA monomer and the MMA-POSS monomer, stirring and mixing uniformly under nitrogen atmosphere, polymerizing and curing at the constant temperature of 65 ℃, and drying the obtained solid in an oven after curing is completed. And (3) placing the dried polymer solid in a fixed bed reactor, heating to 1000 ℃ under an argon atmosphere, preserving heat for 6 hours, and carbonizing the obtained polymer solid. And (3) placing the carbonized intermediate in a 1M HF solution to react for 6 hours at 45 ℃, etching the silicon oxide component, filtering, washing with deionized water for three times, and collecting the solid obtained after filtering to obtain the prepared porous carbon precursor material.
Comparative example 1
Adding MMA monomer and MMA-POSS monomer into a reaction bottle according to the mol ratio of 5:1, adding 0.5% AIBN of the sum of the mol numbers of the MMA monomer and the MMA-POSS monomer, stirring and mixing uniformly under nitrogen atmosphere, polymerizing and curing at the constant temperature of 65 ℃, and drying the obtained solid in an oven after curing is completed. And (3) placing the dried polymer solid in a fixed bed reactor, heating to 1000 ℃ under an argon atmosphere, preserving heat for 6 hours, and carbonizing the obtained polymer solid. And (3) placing the carbonized intermediate in a 1MHF solution to react for 6 hours at 45 ℃, etching the silicon oxide component, filtering, washing with deionized water for three times, and collecting the solid obtained after filtering to obtain the prepared porous carbon precursor material.
Comparative example 2
Adding MMA monomer and MMA-POSS monomer into a reaction bottle according to the mol ratio of 5000:1, adding 0.5% AIBN of the sum of the mol numbers of the MMA monomer and the MMA-POSS monomer, stirring and mixing uniformly under nitrogen atmosphere, polymerizing and curing at the constant temperature of 65 ℃, and drying the obtained solid in an oven after curing is completed. And (3) placing the dried polymer solid in a fixed bed reactor, heating to 1000 ℃ under an argon atmosphere, preserving heat for 6 hours, and carbonizing the obtained polymer solid. And (3) placing the carbonized intermediate in a 1M HF solution to react for 6 hours at 45 ℃, etching the silicon oxide component, filtering, washing with deionized water for three times, and collecting the solid obtained after filtering to obtain the prepared porous carbon precursor material.
Comparative example 3
Adding MMA monomer into a reaction bottle, adding 0.5% AIBN of the sum of mole numbers of the MMA monomer, stirring and mixing uniformly under nitrogen atmosphere, polymerizing and curing at a constant temperature of 65 ℃, and drying the obtained solid in an oven after curing is completed. And (3) placing the dried polymer solid in a fixed bed reactor, heating to 1000 ℃ under an argon atmosphere, preserving heat for 6 hours, and carbonizing the obtained polymer solid. And (3) placing the carbonized intermediate in a 1M HF solution to react for 6 hours at 45 ℃, etching the silicon oxide component, filtering, washing with deionized water for three times, and collecting the solid obtained after filtering to obtain the prepared porous carbon precursor material.
Performance testing
A schematic diagram of the porous carbon precursor material obtained by etching the intermediate with a hydrofluoric acid solution in the above examples is shown in fig. 1, and BET specific surface area tests were performed on the porous carbon precursor materials prepared in the above examples and comparative examples, and specific test results are shown in table I.
Table I BET test results of porous carbon materials obtained in examples and comparative examples
From the BET test results of Table I, it is understood that the pore volume of micropores in the porous carbon materials obtained by adjusting the molar ratio of MMA/MMA-POSS in examples 1 to 8 is relatively large, and that the micropores are mainly derived from post-etching POSS, and thus the pore volume of micropores is closely related to the content of POSS; meanwhile, MMA-POSS is taken as a crosslinking site of a polymer framework, and has direct influence on the molecular structure of the polymer, so that the specific surface area and the total pore volume of the porous carbon are influenced; it can be seen that the porous carbon precursor materials obtained in examples 1-8 have uniform pore sizes and about 1nm in size, and the pore diameters of the prepared porous carbon precursor materials are controllable and regular, so that the prepared silicon carbon material has better electrochemical performance as a negative electrode material of a lithium ion battery. The molar ratio of MMA/MMA-POSS in comparative example 1 is 5/1, so that the molecular skeleton of the obtained polymer is tightly connected, the gaps are smaller, the specific surface area and the total pore volume of the obtained porous after carbonization are smaller, but the micropore pore volume is larger because the POSS component is high; the POSS component has high ratio and is etched away later, so that the porous carbon skeleton obtained in the comparative example 1 has thinner pore wall thickness, and the performance of the prepared material can be influenced; comparative example 3 was free of MMA-POSS, whose polymer was a homopolymer of MMA, and PMMA was melted and then carbonized during carbonization, so that it was very small in pores, resulting in a smaller specific surface area and total pore volume, and, since it contained no POSS, it was substantially free of micropores; the molar ratio MMA/MMA-POSS in comparative example 2 was 5000/1, in which the POSS ratio was already so small that the difference in the micropore volume was small compared to that in comparative example 3.
The above-described embodiments of the present invention do not limit the scope of the present invention. Any of various other corresponding changes and modifications made according to the technical idea of the present invention should be included in the scope of the claims of the present invention.
Claims (10)
1. A method of preparing a porous carbon precursor material, the method comprising the steps of:
s1, mixing a first raw material, a second raw material and a third raw material in a first inert gas atmosphere, and performing polymerization crosslinking to obtain a polymerization crosslinking solid;
the first raw material is polyacrylate POSS, and the chemical formula of the first raw material is as follows:
wherein (1)>
The second raw material is an acrylic ester monomer, and the chemical formula of the second raw material is
The third raw material is azobisisobutyronitrile AIBN;
the molar ratio of the first raw material to the second raw material is (1:20) - (1:4000);
s2, carbonizing the polymerized crosslinked solid in a second inert gas atmosphere to obtain an intermediate;
and S3, placing the intermediate in hydrofluoric acid solution, stirring and soaking, etching the silicon oxide component of the intermediate, precipitating and filtering to obtain the porous carbon precursor material.
2. The method for preparing a porous carbon precursor material according to claim 1, wherein R is 1 The radicals being selected from H, - (CH) 2 ) n CH 3 N is selected from any integer between 0 and 5；R 2 The radicals being selected from H, - (CH) 2 ) n CH 3 N is selected from any integer between 0 and 5; r is R 3 Selected from any one of H, halogen, hydroxyl, cyano, sulfonyl, fluorosulfonyl, sulfonic acid, fluorosulfonyl, saturated or unsaturated alkyl of 1-10 carbon atoms, saturated or unsaturated haloalkyl of 1-10 carbon atoms, alkoxy of 1-10 carbon atoms, or fluoroalkoxy of 1-10 carbon atoms.
3. The method for producing a porous carbon precursor material according to claim 1, wherein a molar ratio of the first raw material to the second raw material is (1:100) to (1:3000);
further preferably, the molar ratio of the first raw material to the second raw material is (1:500) to (1:1500).
4. The method for producing a porous carbon precursor material according to claim 1, wherein the polymerization crosslinking is performed under an oil bath condition of 60 ℃ to 70 ℃, and the first inert gas is nitrogen.
5. The method for preparing a porous carbon precursor material according to claim 1, wherein the second inert gas is argon, the carbonization temperature is 600-1200 ℃, and the carbonization time is 2-8 h.
6. The method for producing a porous carbon precursor material according to claim 1, wherein the concentration of the hydrofluoric acid solution is 0.5M to 1.5M; the pore size of the porous carbon precursor material is less than 1nm.
7. A porous carbon precursor material, characterized in that it is produced by the production method according to any one of claims 1 to 6.
8. A silicon-carbon material prepared from the porous carbon precursor material of claim 7.
9. A lithium ion battery anode material, wherein the anode material comprises a silicon carbon material, and the silicon carbon material is the silicon carbon material of claim 8.
10. A lithium ion battery, characterized in that the lithium ion battery comprises a positive electrode, a negative electrode, electrolyte and a diaphragm, wherein the negative electrode comprises a negative electrode material, and the negative electrode material is the lithium ion battery negative electrode material of claim 9.
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