CN111573651A - Mesoporous carbon material for lithium battery and preparation method thereof - Google Patents
Mesoporous carbon material for lithium battery and preparation method thereof Download PDFInfo
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- CN111573651A CN111573651A CN202010466439.9A CN202010466439A CN111573651A CN 111573651 A CN111573651 A CN 111573651A CN 202010466439 A CN202010466439 A CN 202010466439A CN 111573651 A CN111573651 A CN 111573651A
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 62
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 56
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims abstract description 35
- 229930006000 Sucrose Natural products 0.000 claims abstract description 35
- 239000005720 sucrose Substances 0.000 claims abstract description 35
- 239000013078 crystal Substances 0.000 claims abstract description 24
- 239000002808 molecular sieve Substances 0.000 claims abstract description 23
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229920000642 polymer Polymers 0.000 claims abstract description 21
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 238000000197 pyrolysis Methods 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 235000019820 disodium diphosphate Nutrition 0.000 claims abstract description 12
- GYQBBRRVRKFJRG-UHFFFAOYSA-L disodium pyrophosphate Chemical compound [Na+].[Na+].OP([O-])(=O)OP(O)([O-])=O GYQBBRRVRKFJRG-UHFFFAOYSA-L 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- UGWULZWUXSCWPX-UHFFFAOYSA-N 2-sulfanylideneimidazolidin-4-one Chemical compound O=C1CNC(=S)N1 UGWULZWUXSCWPX-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 238000001704 evaporation Methods 0.000 claims abstract description 8
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 8
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 238000005530 etching Methods 0.000 claims abstract description 6
- 238000004140 cleaning Methods 0.000 claims abstract description 3
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 52
- 238000003756 stirring Methods 0.000 claims description 30
- 239000004115 Sodium Silicate Substances 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 26
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 26
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 26
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 14
- 238000009826 distribution Methods 0.000 abstract description 4
- 239000006181 electrochemical material Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 108091006146 Channels Proteins 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000013335 mesoporous material Substances 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- -1 and meanwhile Substances 0.000 description 2
- 238000010000 carbonizing Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229920000428 triblock copolymer Polymers 0.000 description 2
- UAIUNKRWKOVEES-UHFFFAOYSA-N 3,3',5,5'-tetramethylbenzidine Chemical group CC1=C(N)C(C)=CC(C=2C=C(C)C(N)=C(C)C=2)=C1 UAIUNKRWKOVEES-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920000463 Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
Classifications
-
- 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
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/005—Silicates, i.e. so-called metallosilicalites or metallozeosilites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
-
- 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
-
- 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
-
- 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)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a mesoporous carbon material for a lithium battery and a preparation method thereof, and belongs to the technical field of electrochemical materials. Which comprises the following steps: (1) mixing sucrose and graphene oxide, and adding water to prepare a turbid liquid; (2) evaporating the turbid liquid to obtain a sucrose crystal wrapped with graphene; (3) adding the ground sucrose crystals, the mesoporous molecular sieve, the 2-thio-hydantoin and the disodium dihydrogen pyrophosphate into an organic solvent, mixing, performing ultrasonic dispersion, and then performing heating polymerization to obtain a polymer; (4) pyrolyzing the polymer at high temperature in a polar manner under the protection of inert gas to carbonize the polymer and obtain a pyrolysis product; (5) and immersing the pyrolysis product into an etching solution to etch off the mesoporous molecular sieve, and cleaning and drying to obtain the mesoporous carbon material for the lithium battery. The mesoporous carbon material for the lithium battery is simple to prepare, mild in reaction condition and low in requirements on equipment and instruments, and the prepared mesoporous carbon material is uniform in pore size distribution, large in specific surface area and provided with sequential channels.
Description
Technical Field
The invention relates to the technical field of electrochemical materials, in particular to a mesoporous carbon material for a lithium battery and a preparation method thereof.
Background
Porous carbon refers to a carbon material having a pore structure. According to the definition of the international union of pure and applied chemistry, porous carbon materials can be classified into the following three categories according to pore size: the porous carbon material with the pore diameter smaller than 2nm is a microporous carbon material, the porous carbon material with the pore diameter larger than 50nm is a macroporous carbon material, and the porous carbon material with the pore diameter between 2nm and 50nm is a mesoporous carbon material. The mesoporous carbon can be classified into an ordered mesoporous carbon material and a disordered mesoporous carbon material according to whether mesopores are ordered or not.
The ordered mesoporous carbon material is a novel non-silicon-based mesoporous material, has uniform pore diameter, highly ordered pore channel distribution, huge specific surface area and pore volume, and has wide application prospects in the aspects of adsorption, catalysis, biomedicine and the like. The ordered mesoporous carbon material has a large specific surface area, a relatively large pore diameter and a regular pore channel structure, is beneficial to ion enrichment and transmission, has high activity, is easy to modify or functionalize on the surface, and can be rapidly developed into a novel electrochemical material.
At present, S, B, P, F or N can be doped in the ordered mesoporous carbon material to improve the conductivity of the material, and meanwhile, oxygen-containing functional groups can be introduced to the surface of the material, so that the adsorption and redox capabilities of the carbon material are improved. The research on the ordered mesoporous carbon material doped with a single element is carried out, but the ordered mesoporous carbon material doped with multiple elements is difficult because the ordered mesoporous carbon doped with multiple elements usually needs multiple substances to provide corresponding element sources, the preparation process is relatively complex, the preparation cost is further improved, the preparation method is not beneficial to large-scale preparation and application, and the application and development of the ordered mesoporous carbon material are limited.
Disclosure of Invention
The invention aims to provide a mesoporous carbon material for a lithium battery and a preparation method thereof, and aims to solve the problem that the existing preparation process for preparing an ordered mesoporous carbon material doped with multiple elements is complex.
The technical scheme for solving the technical problems is as follows:
a preparation method of a mesoporous carbon material for a lithium battery comprises the following steps:
(1) mixing sucrose and graphene oxide, and adding water to prepare a turbid liquid;
(2) evaporating the turbid liquid to obtain a sucrose crystal wrapped with graphene;
(3) grinding sucrose crystals, adding the ground sucrose crystals, mesoporous molecular sieve, 2-thio-hydantoin and disodium dihydrogen pyrophosphate into an organic solvent, mixing, performing ultrasonic dispersion, and then performing heating polymerization to obtain a polymer;
(4) pyrolyzing the polymer at high temperature in a polar manner under the protection of inert gas to carbonize the polymer and obtain a pyrolysis product;
(5) and immersing the pyrolysis product into an etching solution to etch off the mesoporous molecular sieve, and cleaning and drying to obtain the mesoporous carbon material for the lithium battery.
Further, in a preferred embodiment of the present invention, the step (1) includes the following specific steps: heating, stirring and dissolving sucrose and graphene according to the mass ratio of (5-10):1 at 40-60 ℃, and ultrasonically dispersing for 0.5-1 h.
Further, in a preferred embodiment of the present invention, the step (2) includes the following specific steps: evaporating the suspension at 60-80 deg.C for crystallization to obtain crystal.
Further, in a preferred embodiment of the present invention, the method for preparing the molecular mesoporous sieve in the step (3) comprises the following steps:
(1) dissolving a template agent P123 in water, and adding a dilute hydrochloric acid solution to prepare a template agent P123 acid solution with the concentration of 0.05-0.1 g/mL;
wherein the volume ratio of water to dilute hydrochloric acid is 1: (0.2-0.5);
(2) dissolving sodium silicate into water to prepare a sodium silicate solution with the concentration of 0.3-0.7 g/mL;
(3) adding a part of sodium silicate solution into the template agent P123 acid solution, stirring and reacting for 0.5-1h at 40-60 ℃, adding a TMB and TEOS mixing agent, stirring and reacting for 1-3h, adding the rest part of sodium silicate solution, and continuously stirring and reacting for 4-6h to obtain a mixed solution;
wherein the volume ratio of the template agent P123 acid solution to the sodium silicate solution is 1: (3-4); the addition amount of the TMB and TEOS mixture is 1-5 wt% of the whole reaction solution; the mass ratio of TMB to TEOS is 1: (0.5-0.8);
(4) the mixed solution is heated for 18 to 24 hours at the temperature of between 80 and 120 ℃, dried and roasted for 3 to 6 hours at the temperature of between 500 and 700 ℃ to prepare the molecular mesoporous sieve.
Further, in a preferred embodiment of the present invention, the step (3) specifically includes the following steps: grinding sucrose crystals, a mesoporous molecular sieve, 2-thio-hydantoin and disodium dihydrogen pyrophosphate, wherein the mass ratio of (0.1-0.3) to 1: (0..5-0.8): (0.7-0.9) mixing in an organic solvent, carrying out ultrasonic dispersion for 2-5h, stirring at normal temperature for 5-8h, and carrying out polymerization reaction at 40-80 ℃ for 10-15h to obtain the polymer.
Further, in a preferred embodiment of the present invention, the step (4) specifically includes the following steps: heating for 2-4h at the temperature of 600-900 ℃ under the protection of nitrogen.
Further, in a preferred embodiment of the present invention, the step (5) specifically comprises: stirring the pyrolysis product in 1-3mol/L sodium hydroxide solution at 80-100 deg.C to remove mesoporous molecular sieve, washing, and drying at 60-100 deg.C.
A mesoporous carbon material for a lithium battery is prepared by adopting the preparation method of the mesoporous carbon material for the lithium battery.
The invention has the following beneficial effects:
1. according to the invention, the graphene oxide and the sucrose are dissolved and mixed to prepare the sucrose crystal, the graphene oxide can uniformly grow and attach to the surface of the sucrose crystal, the sucrose crystal is easily and effectively doped into the mesoporous molecular sieve, the sucrose is a carbon-containing organic matter and provides a carbon source for the mesoporous carbon material as the graphene oxide, and the sucrose molecule also has certain viscosity in the dissolving process and can be used as an accelerant to promote the fusion of the sucrose crystal, the mesoporous molecular sieve, the 2-thio-lactoyl urea and the disodium dihydrogen pyrophosphate to obtain a polymer which is more fully mixed, so that the mesoporous carbon material which is more uniform in pore size distribution, large in specific surface area and provided with a sequence channel is finally obtained, and a channel is provided for the storage and diffusion of a large amount of lithium ions.
2. The mesoporous molecular sieve is prepared by mixing sodium silicate and P123, and a TMB and TEOS mixing agent is added as a pore-expanding agent in the preparation process, so that the prepared mesoporous molecular sieve has a regular three-dimensional pore structure, has higher mesoporous volume and specific surface area, and is beneficial to fully entering sucrose crystals, 2-thio-hydantoin and disodium dihydrogen pyrophosphate into the mesoporous molecular sieve to promote the material to form a mesoporous structure.
3. The mesoporous carbon material is doped with S, N and P elements, wherein oxygen-containing functional groups in disodium dihydrogen pyrophosphate can promote the adsorption of the mesoporous material on S, and a three-dimensional network structure formed by carbonizing sucrose and graphene oxide has a binding effect on S, so that the S content of the mesoporous carbon material is increased, and the conductivity of the mesoporous carbon material is improved when the mesoporous carbon material is used as a lithium battery negative electrode material.
4. The mesoporous carbon material for the lithium battery is simple to prepare, mild in reaction condition and low in requirements on equipment and instruments, and the prepared mesoporous carbon material is uniform in pore size distribution, large in specific surface area and provided with sequential channels.
Detailed Description
The principles and features of this invention are described below in conjunction with embodiments, which are included to explain the invention and not to limit the scope of the invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
In the present invention, P123 is a triblock copolymer, and is collectively referred to as: a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer having the molecular formula: PEO-PPO-PEO; TMB is 3,3',5,5' -tetramethyl benzidine; TEOS is tetraethyl orthosilicate. The organic solvent used was isopropanol.
Example 1:
the preparation method of the mesoporous carbon material for a lithium battery according to the embodiment of the present invention includes the following steps:
(1) heating, stirring and dissolving sucrose and graphene at 40 ℃ according to the mass ratio of 5:1, and ultrasonically dispersing for 0.5 h;
(2) evaporating the turbid liquid at 60 ℃ to obtain a sucrose crystal wrapped with graphene;
(3) grinding sucrose crystals, a mesoporous molecular sieve, 2-thio-hydantoin and disodium dihydrogen pyrophosphate according to the mass ratio of 0.1: 1: 0.5: 0.7, mixing the mixture in an organic solvent, performing ultrasonic dispersion for 2 hours, stirring the mixture for 8 hours at normal temperature, and performing polymerization reaction for 10 hours at 40 ℃ to obtain a polymer;
wherein, the preparation method of the molecular mesoporous sieve in the step (3) comprises the following steps:
(1) dissolving a template agent P123 in water, and adding a dilute hydrochloric acid solution to prepare a template agent P123 acid solution with the concentration of 0.05 g/mL;
wherein the volume ratio of water to dilute hydrochloric acid is 1: 0.2;
(2) dissolving sodium silicate into water to prepare a sodium silicate solution with the concentration of 0.3 g/mL;
(3) adding a part of sodium silicate solution into a template agent P123 acid solution, stirring and reacting for 0.5h at 40 ℃, adding a TMB and TEOS mixing agent, stirring and reacting for 1h, adding the rest part of sodium silicate solution, and continuously stirring and reacting for 4h to obtain a mixed solution;
wherein the volume ratio of the template agent P123 acid solution to the sodium silicate solution is 1: 3; the addition amount of the TMB and TEOS mixture is 1 wt% of the whole reaction solution; the mass ratio of TMB to TEOS is 1: 0.5;
(4) and (3) placing the mixed solution at 80 ℃ for 18h, drying, and roasting at 500 ℃ for 3h to obtain the molecular mesoporous sieve.
(4) Heating the polymer at 600 ℃ for 2h under the protection of nitrogen for high-temperature pyrolysis to carbonize the polymer to obtain a pyrolysis product;
(5) and stirring the pyrolysis product in a sodium hydroxide solution with the concentration of 1mol/L at the temperature of 80 ℃ to remove the mesoporous molecular sieve by etching, washing and drying at the temperature of 60 ℃ to obtain the mesoporous carbon material for the lithium battery.
Example 2:
the preparation method of the mesoporous carbon material for the lithium battery comprises the following steps:
(1) heating, stirring and dissolving sucrose and graphene at 50 ℃ according to the mass ratio of 7:1, and ultrasonically dispersing for 0.7 h;
(2) evaporating the turbid liquid at 60-80 ℃ to obtain a graphene-coated sucrose crystal;
(3) grinding sucrose crystals, a mesoporous molecular sieve, 2-thio-hydantoin and disodium dihydrogen pyrophosphate according to the mass ratio of 0.2: 1: 0.7: 0.8, mixing in an organic solvent, performing ultrasonic dispersion for 3 hours, stirring at normal temperature for 6 hours, and performing polymerization reaction at 60 ℃ for 112 hours to obtain a polymer;
wherein, the preparation method of the molecular mesoporous sieve in the step (3) comprises the following steps:
(1) dissolving a template agent P123 in water, and adding a dilute hydrochloric acid solution to prepare a template agent P123 acid solution with the concentration of 0.075 g/mL;
wherein the volume ratio of water to dilute hydrochloric acid is 1: 0.35;
(2) dissolving sodium silicate into water to prepare a sodium silicate solution with the concentration of 0.5 g/mL;
(3) adding a part of sodium silicate solution into a template agent P123 acid solution, stirring and reacting at 50 ℃ for 0.75h, adding a TMB and TEOS mixture, stirring and reacting for 2h, adding the rest part of sodium silicate solution, and continuously stirring and reacting for 5h to obtain a mixed solution;
wherein the volume ratio of the template agent P123 acid solution to the sodium silicate solution is 1: 3.5; the addition amount of the TMB and TEOS mixture is 3 wt% of the whole reaction solution; the mass ratio of TMB to TEOS is 1: 0.6;
(4) and (3) placing the mixed solution at 100 ℃ for 20h, drying, and roasting at 600 ℃ for 4h to obtain the molecular mesoporous sieve.
(4) Heating the polymer at 750 ℃ for 3h under the protection of nitrogen for high-temperature pyrolysis to carbonize the polymer to obtain a pyrolysis product;
(5) and stirring the pyrolysis product in a sodium hydroxide solution with the concentration of 2mol/L at the temperature of 90 ℃ to remove the mesoporous molecular sieve by etching, washing and drying at the temperature of 80 ℃ to obtain the mesoporous carbon material for the lithium battery.
Example 3:
the preparation method of the mesoporous carbon material for the lithium battery comprises the following steps:
(1) heating, stirring and dissolving sucrose and graphene at the temperature of 60 ℃ according to the mass ratio of 10:1, and ultrasonically dispersing for 1 h;
(2) evaporating the turbid liquid at 80 ℃ to obtain a sucrose crystal wrapped with graphene;
(3) grinding sucrose crystals, a mesoporous molecular sieve, 2-thio-hydantoin and disodium dihydrogen pyrophosphate according to the mass ratio of 0.3: 1: 0.8: 0.9, mixing in an organic solvent, carrying out ultrasonic dispersion for 5 hours, stirring at normal temperature for 8 hours, and carrying out polymerization reaction at 80 ℃ for 15 hours to obtain a polymer;
wherein, the preparation method of the molecular mesoporous sieve in the step (3) comprises the following steps:
(1) dissolving a template agent P123 in water, and adding a dilute hydrochloric acid solution to prepare a template agent P123 acid solution with the concentration of 0.1 g/mL;
wherein the volume ratio of water to dilute hydrochloric acid is 1: 0.5;
(2) dissolving sodium silicate into water to prepare a sodium silicate solution with the concentration of 0.7 g/mL;
(3) adding part of sodium silicate solution into template agent P123 acid solution, stirring and reacting for 1h at 60 ℃, adding TMB and TEOS mixing agent, stirring and reacting for 3h, adding the rest part of sodium silicate solution, and continuing stirring and reacting for 6h to obtain mixed solution;
wherein the volume ratio of the template agent P123 acid solution to the sodium silicate solution is 1: 4; the addition amount of the TMB and TEOS mixture is 5 wt% of the whole reaction solution; the mass ratio of TMB to TEOS is 1: 0.8;
(4) and (3) reacting the mixed solution at 120 ℃ for 24 hours, drying, and roasting at 700 ℃ for 6 hours to obtain the molecular mesoporous sieve.
(4) Heating the polymer at 900 ℃ for 4h under the protection of nitrogen for high-temperature pyrolysis to carbonize the polymer to obtain a pyrolysis product;
(5) and stirring the pyrolysis product in a sodium hydroxide solution with the concentration of 3mol/L at the temperature of 100 ℃ to remove the mesoporous molecular sieve by etching, washing and drying at the temperature of 100 ℃ to obtain the mesoporous carbon material for the lithium battery.
Comparative example 1
The difference between the preparation method of the mesoporous carbon material for the lithium battery of the comparative example and the preparation method of example 1 is that the steps (1) and (2) are reduced, sucrose crystals are not added, and the rest steps are the same as those of example 1.
Comparative example 2
The difference between the preparation method of the mesoporous carbon material for the lithium battery of the comparative example and the preparation method of the example 1 is that the mesoporous molecular sieve used is a commercially common SBA-15 mesoporous molecular sieve.
Analysis of results
Elemental analysis and X-ray photoelectron spectroscopy were performed on the mesoporous carbon materials obtained in examples 1 to 3 and comparative examples 1 to 2, and the results are shown in the following table:
TABLE 1 elemental analysis results of examples 1 to 3 and mesoporous carbon materials obtained in comparative examples 1 to 2
As can be seen from the above table, the mesoporous carbon material for lithium battery prepared in this example has a relatively high nitrogen and sulfur content. The reason is that the oxygen-containing functional group in the disodium dihydrogen pyrophosphate can promote the mesoporous material to adsorb S, and the three-dimensional network structure formed by carbonizing the sucrose and the graphene oxide has a binding effect on S, so that the S content of the mesoporous carbon material is increased.
The mesoporous carbon material for the lithium battery prepared in the embodiment 3 is applied to the lithium battery, and the performance test is as follows:
the CR2025 coin half cell assembly was completed in a glove box under argon atmosphere. The mesoporous carbon material prepared in example 3, polyvinylidene fluoride (PVDF), and a conductive agent (super P) were mixed in N-methylpyrrolidone at a ratio of 75:15:15, and the above mixed solution was uniformly coated on a copper foil having a diameter of 12nm, dried, and pressed into a sheet to obtain a working electrode, and a lithium sheet was used as a reference electrode and a counter electrode. 1M LiPF6/(EC + DMC) (volume ratio 1:1) was the electrolyte and the separator was Celgard (2300). The constant current charge and discharge test adopts certain current density to test the charge and discharge performance of the analog battery, the charge and discharge test voltage interval is 0.0-3.0V, and a secondary battery performance detection system is used for collecting the charge and discharge curve and the capacity of the analog battery. The sweep rate of the cyclic voltammetry test was 0.1mV/S and the voltage period was 0.0-3.0V. Electrochemical impedance test the electrochemical impedance test frequency is from 0.01 to 105 Hz.
The results showed that the charge and discharge capacity of the first turn of the negative electrode material was 2775.89 and 1354.11mA.h.g-1The coulombic efficiency is 48.73 percent, the coulombic efficiency after 50 circles is 98.27 percent, and the highest reversible capacity is 983.35mA.h.g-1The lithium ion battery has high lithium storage and removal performance.
At 500mA.g-1After 200 cycles, the capacity of the negative electrode material obtained in example 3 was 577.85mA.h.g-1It shows that under high current density, better cycle stability can still be maintained.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (8)
1. A preparation method of a mesoporous carbon material for a lithium battery is characterized by comprising the following steps:
(1) mixing sucrose and graphene oxide, and adding water to prepare a turbid liquid;
(2) evaporating the turbid liquid to obtain a sucrose crystal wrapped with graphene;
(3) grinding sucrose crystals, adding the ground sucrose crystals, mesoporous molecular sieve, 2-thio-hydantoin and disodium dihydrogen pyrophosphate into an organic solvent, mixing, performing ultrasonic dispersion, and then performing heating polymerization to obtain a polymer;
(4) carrying out high-temperature pyrolysis on the polymer under the protection of inert gas to carbonize the polymer to obtain a pyrolysis product;
(5) and immersing the pyrolysis product into an etching solution to etch off the mesoporous molecular sieve, and cleaning and drying to obtain the mesoporous carbon material for the lithium battery.
2. The method for preparing a mesoporous carbon material for a lithium battery according to claim 1, wherein the step (1) comprises the following steps: heating, stirring and dissolving sucrose and graphene according to the mass ratio of (5-10):1 at 40-60 ℃, and ultrasonically dispersing for 0.5-1 h.
3. The method for preparing a mesoporous carbon material for a lithium battery according to claim 1, wherein the step (2) comprises the following steps: evaporating the suspension at 60-80 deg.C for crystallization to obtain crystal.
4. The method of preparing a mesoporous carbon material for a lithium battery according to claim 1, wherein the method of preparing the molecular mesoporous sieve in the step (3) comprises the steps of:
(1) dissolving a template agent P123 in water, and adding a dilute hydrochloric acid solution to prepare a template agent P123 acid solution with the concentration of 0.05-0.1 g/mL;
wherein the volume ratio of water to dilute hydrochloric acid is 1: (0.2-0.5);
(2) dissolving sodium silicate into water to prepare a sodium silicate solution with the concentration of 0.3-0.7 g/mL;
(3) adding a part of sodium silicate solution into the template agent P123 acid solution, stirring and reacting for 0.5-1h at 40-60 ℃, adding a TMB and TEOS mixing agent, stirring and reacting for 1-3h, adding the rest part of sodium silicate solution, and continuously stirring and reacting for 4-6h to obtain a mixed solution;
wherein the volume ratio of the template agent P123 acid solution to the sodium silicate solution is 1: (3-4); the addition amount of the TMB and TEOS mixture is 1-5 wt% of the whole reaction solution; the mass ratio of TMB to TEOS is 1: (0.5-0.8);
(4) the mixed solution is heated for 18 to 24 hours at the temperature of between 80 and 120 ℃, dried and roasted for 3 to 6 hours at the temperature of between 500 and 700 ℃ to prepare the molecular mesoporous sieve.
5. The method for preparing a mesoporous carbon material for a lithium battery according to claim 1, wherein the step (3) comprises the following steps: grinding sucrose crystals, mixing with a mesoporous molecular sieve, 2-thio-hydantoin and disodium dihydrogen pyrophosphate according to the mass ratio of (0.1-0.3) 1: (0..5-0.8): (0.7-0.9) mixing in an organic solvent, carrying out ultrasonic dispersion for 2-5h, stirring at normal temperature for 5-8h, and carrying out polymerization reaction at 40-80 ℃ for 10-15h to obtain the polymer.
6. The method for preparing a mesoporous carbon material for a lithium battery according to any one of claims 1 to 5, wherein the step (4) comprises the following steps: heating for 2-4h at the temperature of 600-900 ℃ under the protection of nitrogen.
7. The method for preparing a mesoporous carbon material for a lithium battery according to claim 6, wherein the step (5) comprises the following steps: stirring the pyrolysis product in 1-3mol/L sodium hydroxide solution at 80-100 deg.C to remove mesoporous molecular sieve, washing, and drying at 60-100 deg.C.
8. A mesoporous carbon material for lithium batteries, which is produced by the method for producing a mesoporous carbon material for lithium batteries according to any one of claims 1 to 7.
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