CN113823773B - Size-controllable carbon cage material and preparation method and application thereof - Google Patents

Size-controllable carbon cage material and preparation method and application thereof Download PDF

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CN113823773B
CN113823773B CN202010567148.9A CN202010567148A CN113823773B CN 113823773 B CN113823773 B CN 113823773B CN 202010567148 A CN202010567148 A CN 202010567148A CN 113823773 B CN113823773 B CN 113823773B
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carbon cage
size
controllable
electrochemical
combination
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CN113823773A (en
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邱雄鹰
孔德斌
智林杰
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National Center for Nanosccience and Technology China
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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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • 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
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/387—Tin or alloys based on tin
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention provides a carbon cage material with controllable size, a preparation method and application thereof, wherein the preparation method of the carbon cage material comprises the following steps: (1) Expanding the electrochemical expansion active material under the action of electrolyte by an electrochemical method to obtain an expansion core; (2) Coating the surface of the expansion core obtained in the step (1) by adopting a precursor material to obtain a coating; (3) Carbonizing the coating obtained in the step (2) to obtain the carbon cage material with controllable size; the size of the expansion core is accurately controllable by selecting a proper electrochemical expansion active material, a controllable electrochemical method and proper technological parameters, so that the carbon cage structure with different controllable sizes is realized, the preparation process is simple and flexible, only one controllable electrochemical system is needed to control the sizes of a plurality of carbon cage materials, a plurality of templates or matrixes are not needed to control, and the carbon cage structure has wide application prospect.

Description

Size-controllable carbon cage material and preparation method and application thereof
Technical Field
The invention belongs to the field of materials, and relates to a carbon cage material with controllable size, and a preparation method and application thereof.
Background
The carbon cage is used as a nano material with high specific surface, high electric conductivity, high heat conduction and high stability and specific pore canal size, is widely researched by academic scientific research and economic market, and has important prospective application value. The carbon cage material is used as one of carbon materials and is widely applied to the emerging fields of catalysis, energy storage, filtration, heat exchange, gas or liquid adsorption, electromagnetic shielding, radar stealth and the like.
The carbon cage size controllable preparation technology is taken as a basic technology in the aspect of carbon cage application construction, and is urgently required to develop a simple, quick and well-controllable carbon cage preparation technology under the application demands of a large number of fields at present. Thus, the pore structure and the size of the carbon cage material are gradually developed from the original disorder and the single-unit to the current order and the size controllability. The controllable preparation carbon cage technology of size has very big improvement controllability and practicality that carbon cage was prepared, can promote the quick application of carbon cage material in relevant field to a certain extent.
The carbon cage preparation technique generally employs two methods, the first: the method (CN 108622893A) adopts a foaming agent, firstly, a macromolecule or a polymerizable monomer is mixed with the foaming agent, a macromolecule material with a porous structure is formed by low-temperature foaming, and then porous carbon cages are prepared by high-temperature annealing, carbonization, graphitization and other ways. Second kind: the method of template (CN 108584908B) is adopted, polymer or polymerizable monomer is firstly mixed with template material (template is core), then high temperature annealing, carbonization, graphitization and other ways are carried out to prepare carbon material with template material as core, and then specific post treatment is carried out to remove core template, thus obtaining carbon cage material. The size of the carbon cage material prepared by the method is limited by the size of the template, only one carbon cage material can be prepared by the same template, and the method has small expansibility, namely, the preparation of carbon cage structures with different sizes requires the mixing of a plurality of template materials with different sizes, so that the yield of the carbon cage material prepared by the method is low.
Therefore, it is necessary to develop a method for preparing a size-controllable carbon cage material.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a carbon cage material with controllable size, a preparation method and application thereof, and the size of an expansion inner core is accurately controllable by selecting a proper electrochemical expansion active material, a controllable electrochemical method and proper technological parameters, so that the carbon cage structure with controllable different sizes is realized, the preparation process is simple and flexible, only one controllable electrochemical system is needed to control the sizes of a plurality of carbon cage materials, a plurality of templates or matrixes are not needed to control, and the carbon cage material has wide application prospect.
To achieve the purpose, the invention adopts the following technical scheme:
the invention aims to provide a preparation method of a carbon cage material with controllable size, which comprises the following steps:
(1) Expanding the electrochemical expansion active material under the action of electrolyte by an electrochemical method to obtain an expansion core;
(2) Coating the surface of the expansion core obtained in the step (1) by adopting a precursor material to obtain a coating;
(3) Carbonizing the coating obtained in the step (2) to obtain the carbon cage material with the controllable size.
In the invention, the size of the expansion inner core is accurately controllable by selecting a proper electrochemical expansion active material, a controllable electrochemical method and proper technological parameters, so that the carbon cage structure with different controllable sizes is realized, the preparation process is simple and flexible, only one controllable electrochemical system is needed to control the sizes of a plurality of carbon cage materials, a plurality of templates or matrixes are not needed to control, and the carbon cage structure has wide application prospect.
In the invention, when the controllable electrochemical method is carried out, electrolyte is selected, and in the electrochemical regulation and control process, the electrochemical expansion active material is not contacted with the electrode, but only contacted with the electrolyte, thus greatly simplifying the post-treatment process.
The electrochemical expansion active material is expanded by an electrochemical method to obtain an expansion core, then a precursor is coated on the surface of the expansion core, and then carbonization is carried out to form the carbon cage material with a core-shell structure, so that the carbon cage material can be used as a carbon material in the fields of catalysis, energy storage, filtration, heat exchange, gas adsorption, liquid adsorption, electromagnetic shielding, radar stealth and the like.
In the present invention, the electrochemically expanding active material of step (1) comprises 85-100% by mass (e.g., 85%, 88%, 90%, 92%, 95%, 98%, 100%, etc.) of active component and 0-15% (e.g., 0%, 2%, 5%, 7%, 10%, 12%, 15%, etc.) of conductive agent; by controlling the addition amounts of the electrochemical expansion active material and the conductive agent, the electrochemical expansion active material can realize better expansion rate, and when the addition amount of the electrochemical expansion active material is too low, no obvious volume change exists under the electrochemical action.
In the present invention, the active component includes any one or a combination of at least two of a silicon-based material, a tin-based material, a sulfur-based material, a vanadium-based material, or an iron-based material.
In the present invention, the silicon-based material includes any one or a combination of at least two of silicon, silicon oxide, silicon carbide, magnesium silicide, or silicon nitride.
In the present invention, the tin-based material includes any one or a combination of at least two of tin, tin oxide, stannous oxide, and tin sulfide.
In the present invention, the sulfur-based material includes elemental sulfur and/or sulfur-carbon composite.
In the present invention, the vanadium-based material includes vanadium oxide and/or vanadium sulfide.
In the present invention, the iron-based material includes any one or a combination of at least two of ferroferric oxide, ferrous oxide, or ferric sulfide.
In the present invention, the average particle diameter of the active component is nano-scale and/or micro-scale.
The selection and size of the specific active ingredients are not particularly limited in the present invention, and can be adjusted according to actual needs by those skilled in the art.
In the present invention, the conductive agent includes any one or a combination of at least two of conductive carbon black, graphite, carbon nanotube, graphene or conductive polymer, wherein the graphite is small-sized graphite, preferably graphite having a particle diameter of less than 50nm, such as 50nm, 45nm, 40nm, 35nm, 30nm, 25nm, 20nm, 15nm, 10nm, 5nm, etc.
In the present invention, the conductive polymer includes an ion-based conductive polymer and/or an electron-based conductive polymer (wherein the ion-based conductive polymer includes, but is not limited to, any one or a combination of at least two of polyethylene oxide, polypropylene oxide, polyethylene succinate, polyethylene sebacate, or polyethylene imine, and the electron-based conductive polymer includes, but is not limited to, at least one or a combination of at least two of polyacetylene, polyphenyl, polythiophene, polypyrrole, polyaniline, or polyphenylacetylene).
In the present invention, the method for preparing the electrochemically expandable active material of step (1) includes: and mixing the active component and the conductive agent to obtain the electrochemical expansion active material.
In the present invention, the mixing means includes any one or a combination of at least two of ball milling, mechanical stirring, spray drying, ultrasonic pulverization or high-energy compounding.
In the present invention, the mixing temperature is 25-50 ℃, e.g., 25 ℃, 28 ℃, 30 ℃, 32 ℃, 35 ℃, 38 ℃, 40 ℃, 42 ℃, 45 ℃, 47 ℃,50 ℃, etc., and the mixing time is 30-240min, e.g., 30min, 50min, 70min, 100min, 120min, 150min, 170min, 200min, 220min, 240min, etc.
In the present invention, the electrochemically expandable active material of step (1) has a particle size of 0.01 to 1. Mu.m, for example, 0.01. Mu.m, 0.03. Mu.m, 0.05. Mu.m, 0.08. Mu.m, 0.1. Mu.m, 0.3. Mu.m, 0.5. Mu.m, 0.8. Mu.m, 1. Mu.m, etc.
In the present invention, the electrolyte of step (1) includes a metal salt and an organic solvent.
In the present invention, the metal salt includes LiPF 6 、LiClO 4 、LiTSFI、LiBOB、NaPF 6 、NaClO 4 NaTSFI or ZnSO 4 Any one or a combination of at least two of these.
In the present invention, the concentration of the metal salt is 0.5 to 2mol/L, for example, 0.5mol/L, 0.8mol/L, 1mol/L, 1.2mol/L, 1.5mol/L, 1.7mol/L, 2mol/L, etc.
In the present invention, the organic solvent includes any one or a combination of at least two of EC (ethylene carbonate), PC (propylene carbonate), DEC (diethyl carbonate), DMC (dimethyl carbonate), EMC (methylethyl carbonate) or THF (tetrahydrofuran).
In the present invention, the electrolyte further includes an additive.
In the present invention, the additives include, but are not limited to, film forming agents, flame retardants, overcharge protection agents, low temperature performance improving additives, and the like.
In the present invention, the electrochemical method of step (1) includes a constant current mode or a constant voltage mode.
In the present invention, the current of the constant current mode is 0.001-1A (e.g., 0.001A, 0.003A, 0.005A, 0.008A, 0.01A, 0.03A, 0.05A, 0.08A, 0.1A, 0.3A, 0.5A, 0.8A, 1A, etc.), and the voltage is 2.0-0.01V (e.g., 2.0V, 1.8V, 1.5V, 1.2V, 1V, 0.8V, 0.5V, 0.3V, 0.1V, 0.08V, 0.05V, 0.03V, 0.01V, etc.).
In the present invention, the potential of the constant voltage mode is 0.01V, and the constant voltage charging time is 30 to 120min, for example, 30min, 40min, 50min, 60min, 70min, 80min, 90min, 100min, 110min, 120min, etc.
In the present invention, the electrochemical process electrode in step (1) is a bipolar electrode.
In the present invention, the bipolar electrode includes an inert electrode and a metal electrode.
In the present invention, the inert electrode includes a platinum electrode.
In the present invention, the metal electrode includes any one or a combination of at least two of a lithium electrode, a sodium electrode, a zinc electrode, a magnesium electrode, or an aluminum electrode.
In the present invention, the electrochemical method of step (1) comprises placing an electrochemically expanding active material and an electrolyte in a bipolar electrode for expansion.
In the present invention, the operation mode of the electrochemical method includes any one or a combination of at least two of a constant voltage mode, a constant current mode, or a pulse mode, preferably a constant current mode.
In the present invention, the volume of the electrochemically expandable active material after expansion in step (1) is 120-300% of the volume before expansion, for example 120%, 150%, 180%, 200%, 220%, 250%, 280%, 300%, etc.
In the present invention, the precursor material of step (2) includes any one or a combination of at least two of a graphene material, a high molecular polymer material, or a polymerizable monomer material.
In the present invention, the high molecular polymer material includes any one or a combination of at least two of polyacrylonitrile, polystyrene, polyaniline, polymethyl methacrylate, phenolic resin, unsaturated polyester or chitosan.
In the present invention, the polymeric monomer material includes any one or a combination of at least two of benzene, pyrrole, thiophene, glucose, maltose, or cyclodextrin.
In the invention, the mass ratio of the precursor material and the electrochemical expansion active material in the step (2) is (4-1): (1-2), for example, 4:1, 3.5:1.2, 3:1.4, 2.5:1.6, 3:1.8, 3.5:1.9, 4:2, etc., and if the mass ratio of the precursor material to the electrochemical expansion active material is too high, the carbon layer is too thick, and hardening is not easy to disperse after carbonization of the material; if the mass ratio of the two is too low, complete coating cannot be realized, so that the structure is damaged.
In the present invention, the coating means in the step (2) includes any one or a combination of at least two of physical coating, thermal polymerization coating, electrochemical polymerization coating or photopolymerization coating.
In the present invention, the carbonization method in the step (2) includes any one or a combination of at least two of a low-temperature chemical method, a high-temperature graphitization method, a microwave carbonization method, a laser high-energy bombardment method, and a joule heating method, and the high-temperature graphitization method is preferable.
In the present invention, the carbonization temperature of the high-temperature graphitization method is 500 to 2000 ℃, for example 500 ℃, 800 ℃, 1000 ℃, 1200 ℃,1500 ℃, 1700 ℃, 2000 ℃, etc., and the carbonization time is 10min to 10h, for example 10min, 30min, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, etc.
The second purpose of the invention is to provide a preparation method of the carbon cage material with controllable size, which is one of the purposes, so as to obtain the carbon cage material with controllable size.
In the present invention, the carbon cage material is a porous material having a pore diameter of 0.02 to 3 μm, for example, 0.02 μm, 0.05 μm, 0.08 μm, 0.1 μm, 0.3 μm, 0.5 μm, 0.7 μm, 1 μm, 1.2 μm, 1.5 μm, 1.7 μm, 2 μm, 2.2 μm, 2.5 μm, 2.7 μm, 3 μm, or the like.
It is a further object of the present invention to provide a use of a carbon cage material as defined in one of the objects as a carbon material in catalysis, energy storage, filtration, heat exchange, gas adsorption, liquid adsorption, electromagnetic shielding or radar stealth.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the size of the expansion inner core is accurately controllable (the volume before expansion is 120% -300% of the volume after expansion) by selecting a proper electrochemical expansion active material, a controllable electrochemical method and proper technological parameters, so that the carbon cage structure with different sizes is realized, the preparation process is simple and flexible, only one controllable electrochemical system is needed to control the sizes of a plurality of carbon cage materials, a plurality of templates or matrixes are not needed to control, and the carbon cage structure has a wide application prospect.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a method for electrochemically controllably preparing a carbon cage, which comprises the following steps:
(1) Preparing an expandable active material with the particle size of 1 mu m by mechanically stirring 98.0g of silicon material (with the average particle size of 50 nm) and 2.0g of carbon nano tubes at 25 ℃ in a spray drying mode;
(2) 50.0g of the expandable active material having a particle size of 1 μm prepared in step (1) was placed in 50mL of an electrolyte (LiPF) 6 Concentration 0.5mol/L, EMC: DMC: dec=1:1:1), platinum metal as inert electrode, lithium foil electrode as active electrode. The electrochemical expandable material is obtained by adopting a constant current charging mode and the voltage range is 2.0V-0.01V, and then through the modes of filtering, centrifuging, washing and the like, the size of the electrochemical expandable material is 3 mu m.
(3) 10.0g of the material prepared in the step (2) is mixed with 5.0g of graphene oxide material, and carbonized for 4 hours at 1500 ℃ to obtain the carbon cage material with the pore size distribution of 3 mu m.
The volume of the expandable active material after expansion in this example was 300% of the volume before expansion.
The scanning electron microscope test (model Hitachi S-4800 type field emission scanning electron microscope) performed on the carbon cage material in this example revealed that: the carbon cage material is of a porous structure, the size uniformity of the porous structure is good, and the average size of the porous structure is 2.9 mu m.
In the preparation process of the carbon cage material, the condition of hole collapse does not occur through high-temperature calcination.
Example 2
The embodiment provides a method for electrochemically controllably preparing a carbon cage, which comprises the following steps:
(1) Preparing an expandable active material with the particle size of 10nm by ball milling 90.0g of silicon material (with the average particle size of 5 nm) and 10.0g of conductive carbon black for 30 min;
(2) 50.0g of the expandable active material having a particle size of 10nm prepared in step (1) was placed in 100mL of electrolyte (LiPF) 6 Concentration 2mol/L, EMC: dmc=1:1), platinum metal as inert electrode, lithium foil electrode as active electrode. And the electrochemical expandable material is obtained by adopting a constant current charging mode and a voltage range of 2.0V-0.3V, and then through filtering, centrifuging, washing and other modes, the size of the electrochemical expandable material is 15nm.
(3) And (3) mixing the material prepared in the step (2) with a graphene material, and carbonizing for 10 hours at 500 ℃ to obtain the carbon cage material with the pore size distribution of 20nm.
The volume of the expandable active material after expansion in this example was 150% of the volume before expansion.
The scanning electron microscope test (model Hitachi S-4800 type field emission scanning electron microscope) performed on the carbon cage material in this example revealed that: the carbon cage material is of a porous structure, the size uniformity of the porous structure is good, and the average size of the porous structure is 20nm.
In the preparation process of the carbon cage material, the condition of hole collapse does not occur through high-temperature calcination.
Example 3
The embodiment provides a method for electrochemically controllably preparing a carbon cage, which comprises the following steps:
(1) 50.0g of tin material (particle size 75 nm) was placed as an expandable active material in 200mL of electrolyte (LiPF) 6 Concentration 1mol/L, EMC: dmc=1:1), platinum metal as inert electrode, lithium foil electrode as active electrode. And the electrochemical expandable material is obtained by adopting a constant current charging mode and a voltage range of 2.0V-0.01V, and then through filtering, centrifuging, washing and other modes, the size of the electrochemical expandable material is 150nm.
(2) 2.0g of the material prepared in the step (1) was mixed with 8.0g of polyacrylonitrile (weight average molecular weight 200000), and carbonized at 2000℃for 30 minutes by Joule heat, to obtain a carbon cage material having a pore size distribution of 150nm.
The volume of the expandable active material after expansion in this example was 200% of the volume before expansion.
The scanning electron microscope test (model Hitachi S-4800 type field emission scanning electron microscope) performed on the carbon cage material in this example revealed that: the carbon cage material is of a porous structure, the size uniformity of the porous structure is good, and the average size of the porous structure is 155nm.
In the preparation process of the carbon cage material, the condition of hole collapse does not occur through high-temperature calcination.
Example 4
The embodiment provides a method for electrochemically controllably preparing a carbon cage, which comprises the following steps:
(1) Preparing an expandable active material with the particle size of 250nm by mechanically stirring 85g of a sulfur material (with the average particle size of 200 nm) and 10g of conductive carbon black for 1 h;
(2) 50g of the expandable active material having a particle size of 250nm prepared in step (1) was placed in 200mL of an electrolyte (NaPF) 6 Concentration 1.0mol/L, EMC: dmc=1:1), platinum metal as inert electrode, sodium foil electrode as active electrode. And the electrochemical expandable material is obtained by adopting a constant current charging mode and a voltage range of 2.0V-0.1V, and then through filtering, centrifuging, washing and other modes, the size of the electrochemical expandable material is 300nm (volume change is 120%).
(3) Mixing the material prepared in the step (2) with a melamine material, carbonizing for 1h at 600 ℃, and then carrying out microwave treatment for 10min to obtain the carbon cage material with the particle size of 300 nm.
The volume of the expandable active material after expansion in this example was 120% of the volume before expansion.
The scanning electron microscope test (model Hitachi S-4800 type field emission scanning electron microscope) performed on the carbon cage material in this example revealed that: the carbon cage material is of a porous structure, the size uniformity of the porous structure is good, and the average size of the porous structure is 310nm.
In the preparation process of the carbon cage material, the condition of hole collapse does not occur through high-temperature calcination.
Example 5
By adopting the electrochemical method in example 1, the volume expansion rate (120%, 150%, 180%, 200%, 250%, 300%, structural failure) of the expandable active material can be controlled by controlling the addition amounts of the silicon material and the carbon nanotubes in the same manner as in example 1 by adjusting the addition amounts of 85.0g to 15.0g, 88.0g to 12.0g, 90.0g to 10.0g, 92.0g to 8.0g, 95.0g to 5.0g, 98.0g to 2.0g, 100.0g to 0.0g in this order.
The scanning electron microscope test (model Hitachi S-4800 type field emission scanning electron microscope) performed on the carbon cage material in this example revealed that: the carbon cage material is of a porous structure, and the size uniformity of the porous structure is good under the condition of different adding proportions.
In the preparation process of the carbon cage material, the condition of hole collapse does not occur through high-temperature calcination.
Example 6
Using the electrochemical process of example 1, the voltage process parameters of the electrochemical process were adjusted to range from 2.0V to 1.8V, from 2.0V to 1.5V, from 2.0V to 1.0V, from 2.0V to 0.5V, from 2.0V to 0.2V, from 2.0V to 0.1V, from 2.0V to 0.05V, from 2.0V to 0.02V, from 2.0V to 0.01V, and the remaining steps were the same as in example 1, and it was found that the volume expansion rate (120%, 130%, 140%, 150%, 180%, 200%, 250%, 280%, 300%) of the expandable active material could be controlled by controlling different voltage ranges.
The scanning electron microscope test (model Hitachi S-4800 type field emission scanning electron microscope) performed on the carbon cage material in this example revealed that: the carbon cage material is of a porous structure, and the uniformity of the size of the porous structure is good under the condition of adjusting different process parameters.
In the preparation process of the carbon cage material, the condition of hole collapse does not occur through high-temperature calcination.
Example 7
The difference from example 1 is only that the sum of the addition amounts of the material prepared in step (2) and the graphene oxide material is the same as example 1, but the mass ratio of the two is 5:1, and the rest of the preparation methods are the same as example 1.
The volume of the expandable active material after expansion in this example was 300% of the volume before expansion.
The scanning electron microscope test (model Hitachi S-4800 type field emission scanning electron microscope) performed on the carbon cage material in this example revealed that: through high-temperature calcination, the carbon cage material is porous structure with nonuniform size, and large-area hole collapse occurs.
Example 8
The difference from example 1 is only that the sum of the addition amounts of the material prepared in step (2) and the graphene oxide material is the same as example 1, but the mass ratio of the two is 1:5, and the rest of the preparation methods are the same as example 1.
The volume of the expandable active material after expansion in this example was 300% of the volume before expansion.
The scanning electron microscope test (model Hitachi S-4800 type field emission scanning electron microscope) performed on the carbon cage material in this example revealed that: through high-temperature calcination, the carbon cage material is in a compact and hardened structure, and is macroscopically hard and cannot be dispersed.
Comparative example 1
The only difference from example 1 is that electrochemical methods of the swellable active material are not included, and the remaining composition and preparation method are the same as example 1.
The volume of the expandable active material after expansion in this example is 100% of the volume before expansion.
As demonstrated by the comparison of example 1 and comparative example 1, expansion cannot be performed without electrochemical methods on the expandable active material.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.

Claims (30)

1. The preparation method of the carbon cage material with the controllable size is characterized by comprising the following steps of:
(1) Expanding the electrochemical expansion active material under the action of electrolyte by an electrochemical method to obtain an expansion core;
(2) Coating the surface of the expansion core obtained in the step (1) by adopting a precursor material to obtain a coating;
(3) Carbonizing the coating obtained in the step (2) to obtain the carbon cage material with controllable size;
the electrochemical expansion active material in the step (1) comprises 85-100% of active components and 0-15% of conductive agents in percentage by mass;
the electrochemical method in the step (1) comprises a constant-current mode or a constant-voltage mode;
the current of the constant current mode is 0.001-1A, and the voltage is 2.0-0.01V;
the potential of the constant voltage mode is 0.01-V, and the constant voltage charging time is 30-120 min;
the volume of the electrochemically expanding active material after expansion in the step (1) is 120-300% of the volume before expansion;
the precursor material in the step (2) comprises any one or a combination of at least two of a graphene material, a high-molecular polymer material or a polymerizable monomer material;
the mass ratio of the precursor material to the electrochemical expansion active material in the step (2) is (4-1) to (1-2).
2. The method of claim 1, wherein the active component comprises any one or a combination of at least two of a silicon-based material, a tin-based material, a sulfur-based material, a vanadium-based material, and an iron-based material.
3. The method of claim 2, wherein the silicon-based material comprises any one or a combination of at least two of silicon, silicon oxide, silicon carbide, magnesium silicide, and silicon nitride.
4. The method of making a size controllable carbon cage material of claim 2 wherein the tin-based material comprises any one or a combination of at least two of tin, tin oxide, stannous oxide or tin sulfide.
5. The method of making a size controllable carbon cage material of claim 2 wherein the sulfur-based material comprises elemental sulfur and/or sulfur-carbon composite.
6. The method of producing a size controllable carbon cage material according to claim 2, wherein the vanadium-based material comprises vanadium oxide and/or vanadium sulfide.
7. The method of making a size controllable carbon cage material of claim 2 wherein the iron-based material comprises any one or a combination of at least two of ferroferric oxide, ferrous oxide, or ferric sulfide.
8. The method for preparing a size-controllable carbon cage material according to claim 1, wherein the average particle size of the active component is nano-sized and/or micro-sized.
9. The method of claim 1, wherein the conductive agent comprises any one or a combination of at least two of conductive carbon black, graphite, carbon nanotubes, graphene, or conductive polymers.
10. The method of making a size controllable carbon cage material of claim 9 wherein the conductive polymer comprises an ion-based conductive polymer and/or an electron-based conductive polymer.
11. The method for preparing a size controllable carbon cage material according to claim 1, wherein the method for preparing an electrochemically expandable active material according to step (1) comprises: and mixing the active component and the conductive agent to obtain the electrochemical expansion active material.
12. The method of claim 11, wherein the mixing comprises any one or a combination of at least two of ball milling, mechanical stirring, spray drying, ultrasonic pulverization, and high energy compounding.
13. The method for preparing a size controllable carbon cage material according to claim 11, wherein the mixing temperature is 25-50 ℃ and the mixing time is 30-240 min.
14. The method for producing a size controllable carbon cage material according to claim 1, wherein the electrochemically expandable active material in step (1) has a particle size of 10nm to 1 μm.
15. The method for preparing a size controllable carbon cage material according to claim 1, wherein the electrolyte in step (1) comprises a metal salt and an organic solvent.
16. The method of making a size controllable carbon cage material of claim 15 wherein the metal salt comprises LiPF 6 、LiClO 4 、LiTSFI、LiBOB、NaPF 6 、NaClO 4 NaTSFI or ZnSO 4 Any one or a combination of at least two of these.
17. The method for preparing a size controllable carbon cage material according to claim 15, wherein the concentration of the metal salt is 0.5-2 mol/L.
18. The method of making a size controllable carbon cage material of claim 15 wherein the organic solvent comprises any one or a combination of at least two of EC, PC, DEC, DMC, EMC or THF.
19. The method for preparing a carbon cage material with controllable size according to claim 1,
the electrode for electrochemical method in the step (1) is a bipolar electrode.
20. The method of making a size controllable carbon cage material of claim 19 wherein the bipolar electrode comprises an inert electrode and a metal electrode.
21. The method of making a size controllable carbon cage material of claim 20 wherein the inert electrode comprises a platinum electrode.
22. The method of claim 20, wherein the metal electrode comprises any one or a combination of at least two of a lithium electrode, a sodium electrode, a zinc electrode, a magnesium electrode, and an aluminum electrode.
23. The method of claim 1, wherein the electrochemical process of step (1) comprises placing an electrochemically expanding active material and an electrolyte in a bipolar electrode for expansion.
24. The method for preparing a carbon cage material with controllable size according to claim 1, wherein the operation mode of the electrochemical method comprises any one or a combination of at least two of a constant voltage mode, a constant current mode or a pulse mode.
25. The method for preparing a carbon cage material with controllable size according to claim 1,
the high polymer material comprises any one or a combination of at least two of polyacrylonitrile, polystyrene, polyaniline, polymethyl methacrylate, phenolic resin, unsaturated polyester or chitosan.
26. The method of making a size controllable carbon cage material of claim 1 wherein the polymerizable monomer material comprises any one or a combination of at least two of benzene, pyrrole, thiophene, glucose, maltose, or cyclodextrin.
27. The method of claim 1, wherein the coating in step (2) comprises any one or a combination of at least two of physical coating, thermal polymerization coating, electrochemical polymerization coating, or photopolymerization coating.
28. The method of claim 1, wherein the carbonization in step (2) comprises any one or a combination of at least two of a low temperature chemical process, a high temperature graphitization process, a microwave carbonization process, a laser high energy bombardment process, and a joule heating process.
29. The method of claim 28, wherein the carbonization in step (2) is performed by high temperature graphitization.
30. The method for preparing a carbon cage material of controllable size of claim 28, wherein the carbonization temperature of the high temperature graphitization method is 500-2000 ℃ and the carbonization time is 10min-10 h.
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