CN112467109A - Activated carbon material, composite material, cathode material and cathode sheet of zinc ion energy storage device and zinc ion energy storage device - Google Patents

Activated carbon material, composite material, cathode material and cathode sheet of zinc ion energy storage device and zinc ion energy storage device Download PDF

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CN112467109A
CN112467109A CN202011359254.4A CN202011359254A CN112467109A CN 112467109 A CN112467109 A CN 112467109A CN 202011359254 A CN202011359254 A CN 202011359254A CN 112467109 A CN112467109 A CN 112467109A
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carbon material
activated carbon
zinc
energy storage
storage device
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方钊
黄文龙
彭嘉鑫
侯雪阳
李林波
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Xian University of Architecture and Technology
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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
    • 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
    • C01B32/30—Active carbon
    • 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
    • C01B32/30—Active carbon
    • C01B32/312—Preparation
    • 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
    • C01B32/30—Active carbon
    • C01B32/312—Preparation
    • C01B32/342—Preparation characterised by non-gaseous activating agents
    • 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
    • C01B32/30—Active carbon
    • C01B32/312—Preparation
    • C01B32/342—Preparation characterised by non-gaseous activating agents
    • C01B32/348—Metallic compounds
    • 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
    • C01B32/30—Active carbon
    • C01B32/354—After-treatment
    • C01B32/378—Purification
    • 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
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • 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
    • 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
    • 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
    • H01M4/626—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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Abstract

The invention provides an active carbon material, a composite material and a zinc ion energy storage deviceThe cathode material, the cathode sheet and the zinc ion energy storage device are characterized in that the specific surface area of the active carbon material is 1800-2600 m2(ii)/g; the total volume of the pores of the activated carbon material is 1.10-1.70 cm3The volume of micropores with the pore diameter of less than 1nm accounts for 1-13% of the total volume of the pores, the volume of mesopores with the pore diameter of 1-10 nm accounts for 48-58% of the total volume of the pores, and the volume of macropores with the pore diameter of more than 10nm accounts for 29-41% of the total volume of the pores. The active carbon material has a reasonable hierarchical pore structure, is compounded with a metal material, can well limit the metal material in the hierarchical pore structure of the active carbon material, is applied to the cathode of a zinc ion energy storage device, can furthest excite the capacitance performance of the zinc ion energy storage device, and has high capacity and excellent cycle stability.

Description

Activated carbon material, composite material, cathode material and cathode sheet of zinc ion energy storage device and zinc ion energy storage device
Technical Field
The invention relates to the technical field of carbon materials, in particular to an activated carbon material, a composite material, a cathode material and a cathode sheet of a zinc ion energy storage device and the zinc ion energy storage device.
Background
The increasing concern over environmental issues, as well as the need to reduce greenhouse gas emissions, has increased the global demand for economically sustainable energy storage. With the increasing demand of people for electrochemical energy storage devices, limited lithium resources begin to become a key problem that restricts the large-scale application of lithium ion batteries. Therefore, Zinc Ion Batteries (ZIBs) with abundant raw material reserves are beginning to receive much attention in the field of large-scale energy storage. The zinc metal negative electrode has the highest specific capacity in ZIBs electrode materials, and is an ideal anode material, so that the development of safe, environment-friendly and cheap ZIBs cathode energy storage materials is of great significance.
The traditional ZIBs are popular as a novel energy storage device compared with the traditional lithium ion battery, and have the characteristics of higher safety, better environmental friendliness and the like. The charge storage mechanism in the ZIBs depends on the migration of zinc ions between a metal zinc cathode and a metal zinc anode material, and at present, the zinc ion battery anode material mainly comprises: manganese-based oxide, vanadium-based compound, Prussian blue analogue, Co3O4Nanorods, polyaniline, and activated carbon-based materials. The carbon-based material in various electrode materials has obvious advantages compared with other materials due to the high specific surface area, excellent electronic conductivity and the controllability of pore size distribution in the preparation process.
Research finds that carbon-based materials also have a great number of problems as cathode materials for zinc ion batteries. The one-dimensional carbon nano tubes can be interconnected to form a network structure to effectively ensure electron conduction, and a special hollow pipeline structure can be used as a buffer tank structure of working ions in electrolyte to realize rapid transport of the ions, so that excellent multiplying power performance can be obtained easily; however, due to its relatively low specific surface area and density, additional modifications are required in practical applications to achieve high specific capacity requirements. The two-dimensional graphene has a large and open plane, provides a large number of active sites for energy storage, and is easy to agglomerate and self-assemble in the charging and discharging process. Commercial activated carbon is currently the most readily available carbon material because of its mature manufacturing technology and low cost, which has been mass produced. The commercial activated carbon has a single pore channel structure, and the specific surface area of the common activated carbon is 1000-1500 m2In the range of per gram, the pore volume is 0.50-0.80 cm3The/g is mainly formed by matching a single mesoporous aperture with a small number of micropores, and high capacity cannot be realized.
Disclosure of Invention
In view of the above, the present invention provides an activated carbon material, a composite material, a cathode material and a cathode sheet of a zinc ion energy storage device, and the activated carbon material has a specific surface area of 1800-2600 m2The total volume of the holes is 1.10-1.70 cm3The high specific surface area and the large pore volume are beneficial to the activated carbon material to exert the advantages of the reaction active sites of the specific surface area and the high energy storage advantages of the large pore volume; in addition, the pores of the activated carbon material comprise micropores with the pore diameter of less than 1nm (the volume of the micropores accounts for 1-13% of the total volume of the pores), mesopores with the pore diameter of 1-10 nm (the volume of the mesopores accounts for 48-58% of the total volume of the pores), and macropores with the pore diameter of more than 10nm (the volume of the macropores accounts for 29-41% of the total volume of the pores), wherein the micropores guarantee a high specific surface area and more reaction active sites, the mesopores guarantee the charge storage capacity of the activated carbon material, the macropores guarantee the flow of electrolyte and a transmission channel of substances, and the activated carbon material has a reasonable hierarchical pore structure, is compounded with a metal material, can well and canThe metal material is limited in the hierarchical pore structure of the activated carbon material, and the obtained composite material is applied to the cathode of the zinc ion energy storage device, so that the capacitance performance of the zinc ion energy storage device is stimulated to the greatest extent, and the zinc ion energy storage device has high capacity and excellent cycle stability.
In order to achieve the above purpose, the invention provides the following technical scheme:
the activated carbon material has a specific surface area of 1800-2600 m2(ii)/g; the total volume of the pores of the activated carbon material is 1.10-1.70 cm3The volume of micropores with the pore diameter of less than 1nm accounts for 1-13% of the total volume of the pores, the volume of mesopores with the pore diameter of 1-10 nm accounts for 48-58% of the total volume of the pores, and the volume of macropores with the pore diameter of more than 10nm accounts for 29-41% of the total volume of the pores; the activated carbon material also comprises O, F, N, P, S at least one hetero element.
As a further improvement of the above technical solution, the activated carbon material comprises the following element components in percentage by mass, based on 100% of the total mass of the activated carbon material: 78-95% of C element, 5-13% of O element, 0-3% of F element, 0-2% of N element, 0-2.5% of P element and 0-1.5% of S element.
The invention also provides a preparation method of the activated carbon material, which comprises the following steps:
providing woody plant powder;
heating and carbonizing the woody plant powder in a protective atmosphere or a vacuum environment to obtain an active crude carbon material;
and mixing the active coarse carbon material with an activating agent, and heating and activating in a protective atmosphere or a vacuum environment to obtain the active carbon material.
As a further improvement of the technical scheme, the woody plant powder is obtained by crushing woody plants in a crusher with the rotating speed of 30000-35000 r/min;
preferably, the particle size of the woody plant powder is 50-300 meshes;
preferably, the woody plant comprises roots and/or stems of at least one of poplar, phoenix tree, pine, persimmon tree, willow, walnut tree, pomegranate tree and wintergreen;
preferably, the method further comprises, before the temperature-rising carbonization: drying the crushed woody plant;
preferably, the drying temperature is 80-150 ℃, and the drying time is 12-48 h;
preferably, the temperature-rising carbonization and the temperature-rising activation are both carried out in a protective atmosphere;
preferably, the protective atmosphere comprises at least one of argon, nitrogen, helium and neon;
preferably, the temperature-rising carbonization conditions include: heating to 400-600 ℃ at a heating rate of 1-10 ℃/min, and preserving heat for 1-5 h at 400-600 ℃.
As a further improvement of the above technical solution, the activating agent includes at least one of potassium hydroxide, sodium hydroxide, lithium hydroxide, sodium bicarbonate, potassium bicarbonate, lithium carbonate, sodium carbonate, potassium carbonate, ferrous chloride, ferric chloride, copper chloride, cobalt chloride, zinc chloride, phosphoric acid, potassium dihydrogen phosphate, potassium hydrogen sulfate, sodium hydrogen sulfate, calcium hydroxide, phosphorus pentoxide, and zinc trifluoromethanesulfonate;
preferably, the mass ratio of the activated crude carbon material to the activating agent is (1-1.5): (1-2);
preferably, the temperature-rising activation conditions include: heating to 800-1000 ℃ at a heating rate of 1-10 ℃/min, and preserving heat at 800-1000 ℃ for 1-5 h;
as a further improvement of the above technical solution, the preparation method further comprises: carrying out acid washing on the activated carbon material obtained by heating and activating;
preferably, the pickling process comprises: mixing the activated carbon material with an acid solution, and then carrying out solid-liquid separation;
preferably, the volume ratio of the acid solution to the activated carbon material is (150-300): (1-10);
preferably, the acid solution comprises at least one of hydrochloric acid solution, sulfuric acid solution, nitric acid solution, acetic acid solution, perchloric acid solution, hypochlorous acid solution and hydrofluoric acid solution with the concentration of 0.1-1M;
optionally, the mixing mode adopts stirring mixing; preferably, the stirring speed is 500-1200 r/min, and the stirring time is 0.5-2 h;
preferably, the solid-liquid separation comprises at least one of filtration and centrifugation;
preferably, qualitative filter paper with the pore diameter of 20-60 mu m is adopted for filtering;
preferably, the acid washing process further comprises the following steps: washing the activated carbon material after acid washing with water;
preferably, the method further comprises the following steps after water washing: drying the washed activated carbon material; optionally, drying the washed activated carbon material at 60-100 ℃ for 1-24 h.
The invention also provides a composite material containing the activated carbon material.
Further, the composite material further comprises a metal material, wherein the metal material comprises at least one of a metal simple substance and a metal compound;
preferably, the metal simple substance comprises at least one of V, Fe, Co, Mn, Mo, Ni, Cu and Ag; the metal compound comprises an oxide and/or sulfide of at least one of V, Fe, Co, Mn, Mo, Ni, Cu and Ag;
preferably, the particle size of the metal material is 5-500 nm.
As a further improvement of the technical scheme, the mass ratio of the activated carbon material to the metal material is (85-95): (5-15).
The invention also provides a preparation method of the composite material, which comprises the following steps: mixing raw materials including the activated carbon material and the metal material.
As a further improvement of the above technical scheme, the preparation method further comprises the step of carrying out high-energy ball milling treatment on the mixed mixture;
preferably, the conditions of the high-energy ball milling treatment include: the mass ratio of the mixture to the grinding balls is (1-1.5): (100-200), the ball milling speed is 600-1200 r/min, and the ball milling time is 0.5-2 h;
preferably; the grinding balls are grinding balls with the diameter of 1-5 mm and grinding balls with the diameter of 8-10 mm, and the ratio of the total volume of the grinding balls with the diameter of 1-5 mm to the total volume of the grinding balls with the diameter of 8-10 mm is (1-15): (25-50).
The invention also provides a cathode material of a zinc ion energy storage device containing the composite material.
As a further improvement of the above technical solution, the cathode material further comprises a conductive agent and a binder;
preferably, the mass ratio of the composite material to the conductive agent to the binder is (8-9.5): (1-0.2): (1-0.3).
The invention also provides a preparation method of the cathode material of the zinc ion energy storage device, which comprises the following steps: mixing raw materials including the composite material, the conductive agent, and the binder.
The invention also provides a cathode plate of the zinc ion energy storage device, which comprises a current collector and a cathode material layer, wherein the cathode material layer is prepared by coating the cathode material of the zinc ion energy storage device on the current collector;
preferably, the thickness of the cathode sheet is 40-210 μm, and the surface density is 1-5 mg/cm2；
Preferably, the current collector is made of stainless steel.
The invention also provides a preparation method of the cathode sheet of the zinc ion energy storage device, which comprises the following steps:
providing a current collector;
and coating the cathode material on the current collector, and then drying to obtain the cathode material layer.
As a further improvement of the technical scheme, the coating thickness is 50-200 μm;
preferably, the drying comprises pre-drying and post-drying; optionally, the pre-drying temperature is 80-120 ℃, and the time is 20-40 min; the post-drying temperature is 80-120 ℃, and the time is 12-48 h;
preferably, the method further comprises, after the pre-drying and before the post-drying: rolling the pre-dried product;
preferably, the rolling temperature is 100-200 ℃.
The invention also provides a zinc ion energy storage device which comprises the cathode plate.
As a further improvement of the above technical solution, the zinc ion energy storage device further includes an anode sheet and an electrolyte;
preferably, the anode sheet is a zinc foil sheet;
preferably, the electrolyte is an aqueous solution containing zinc ions;
optionally, the electrolyte of the electrolyte is at least one of zinc chloride, zinc sulfate heptahydrate, zinc nitrate hexahydrate, zinc acetate, zinc perchlorate hexahydrate, zinc trifluoromethanesulfonate, zinc citrate, zinc oxalate, zinc borofluoride, zinc dihydrogen phosphate, zinc bromide and zinc iodide;
preferably, the concentration of the electrolyte is 0.5-3M;
preferably, the conductivity of the electrolyte at 25 ℃ is 10.00-30.00 mS/cm.
As a further improvement of the technical scheme, the zinc ion energy storage device is a CR2015 button cell, a CR2025 button cell, a CR2032 button cell or an electrode with the area of 2-10 cm2The aluminum plastic film soft package battery.
The invention has the beneficial effects that:
the specific surface area of the activated carbon material is 1800-2600 m2The total volume of the holes is 1.10-1.70 cm3The high specific surface area and the large pore volume are beneficial to the activated carbon material to exert the advantages of the reaction active sites of the specific surface area and the high energy storage advantages of the large pore volume; in addition, the pores of the activated carbon material comprise micropores with the pore diameter of less than 1nm (the volume of the micropores accounts for 1-13% of the total volume of the pores), mesopores with the pore diameter of 1-10 nm (the volume of the mesopores accounts for 48-58% of the total volume of the pores), and macropores with the pore diameter of more than 10nm (the volume of the macropores accounts for 29-41% of the total volume of the pores), wherein the micropores ensure a high specific surface area and more reaction active sitesThe active carbon material has a reasonable hierarchical pore structure, and is compounded with a metal material, so that the metal material can be well limited in the hierarchical pore structure of the active carbon material, the obtained composite material is applied to a cathode of a zinc ion energy storage device, the volume change of the metal material in the composite material in the alloying reaction process with zinc ions is well inhibited, the capacitance performance of the zinc ion energy storage device is stimulated to the greatest extent, and the zinc ion energy storage device has high capacity and excellent cycle stability.
Drawings
To more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are required to be used in the embodiments will be briefly described below, and it should be understood that the following drawings only illustrate some embodiments of the present invention, and therefore should not be considered as limiting the scope of the present invention.
FIG. 1 is an SEM topography of an activated carbon material prepared in example 1 of the present invention;
FIG. 2 is a nitrogen adsorption and desorption isotherm graph of the activated carbon material prepared in example 1 of the present invention;
FIG. 3 is a BET plot of the activated carbon material prepared in example 1 of the present invention;
FIG. 4 is a CV plot of 1mV/s scan rate for zinc ion energy storage devices prepared in example 1 of the present invention and comparative example 5;
FIG. 5 is a CV plot of zinc ion energy storage devices prepared in example 1 of the present invention at different scan rates of 1mV/s, 5mV/s, 10mV/s and 20 mV/s;
FIG. 6 is a CV plot of the zinc ion energy storage device prepared in comparative example 5 at different scan rates of 1mV/s, 5mV/s, 10mV/s, and 20 mV/s.
Detailed Description
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention.
This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein, but rather should be construed as broadly as the present invention is capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
The terms as used herein:
"prepared from … …" is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of … …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of … …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when the range "1 ~ 5" is disclosed, the ranges described should be construed to include the ranges "1 ~ 4", "1 ~ 3", "1 ~ 2 and 4 ~ 5", "1 ~ 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
In these examples, the parts and percentages are by mass unless otherwise indicated.
"part by mass" means a basic unit of measure indicating a mass ratio of a plurality of components, and 1 part may represent any unit mass, for example, 1g or 2.689 g. If we say that the part by mass of the component A is a part by mass and the part by mass of the component B is B part by mass, the ratio of the part by mass of the component A to the part by mass of the component B is a: b. alternatively, the mass of the A component is aK and the mass of the B component is bK (K is an arbitrary number, and represents a multiple factor). It is unmistakable that, unlike the parts by mass, the sum of the parts by mass of all the components is not limited to 100 parts.
"and/or" is used to indicate that one or both of the illustrated conditions may occur, e.g., a and/or B includes (a and B) and (a or B).
The invention provides an activated carbon material, and the specific surface area of the activated carbon material is 1800-2600 m2(ii)/g; the total volume of the pores of the activated carbon material is 1.10-1.70 cm3/g。
The activated carbon material comprises micropores with the pore diameter of less than 1nm, mesopores with the pore diameter of 1-10 nm and macropores with the pore diameter of more than 10nm, wherein the volume of the micropores with the pore diameter of less than 1nm accounts for 1-13% of the total volume of the pores, the volume of the mesopores with the pore diameter of 1-10 nm accounts for 48-58% of the total volume of the pores, and the volume of the macropores with the pore diameter of more than 10nm accounts for 29-41% of the total volume of the pores.
The activated carbon material has high specific surface area and large pore volume, and is favorable for the activated carbon material to exert the advantages of reaction active sites of the specific surface area and high energy storage of the large pore volume; in addition, the pores of the activated carbon material comprise micropores with the pore diameter of less than 1nm (the volume of the micropores accounts for 1-13% of the total volume of the pores), mesopores with the pore diameter of 1-10 nm (the volume of the mesopores accounts for 48-58% of the total volume of the pores), and macropores with the pore diameter of more than 10nm (the volume of the macropores accounts for 29-41% of the total volume of the pores), wherein the micropores guarantee a high specific surface area and more reactive active sites, the mesopores guarantee the charge storage capacity of the activated carbon material, the macropores guarantee the flow of electrolyte, and a transmission channel of substances.
The activated carbon material also comprises O, F, N, P, S at least one hetero element.
Further, the activated carbon material comprises the following element components in percentage by mass based on the total mass of the activated carbon material as 100 percent: 78-95% of C element, 5-13% of O element, 0-3% of F element, 0-2% of N element, 0-2.5% of P element and 0-1.5% of S element.
The invention also provides a preparation method of the activated carbon material, which comprises the following steps:
providing woody plant powder;
heating and carbonizing woody plant powder in a protective atmosphere or a vacuum environment to obtain an active crude carbon material;
and mixing the active coarse carbon material with an activating agent, and heating and activating in a protective atmosphere or a vacuum environment to obtain the active carbon material.
The woody plant comprises root and/or stem of at least one of poplar, phoenix tree, pine, persimmon tree, willow, walnut tree, pomegranate tree and wintergreen.
Preferably, the woody plant powder is quickly crushed in a crusher with the rotating speed of 30000-35000 r/min; preferably, the woody plant is crushed into powder with the particle size of 50-300 meshes, so that subsequent carbonization and activation are facilitated.
Preferably, the method further comprises, before the temperature-raising carbonization: drying the crushed woody plant; preferably, the drying temperature is 80-150 ℃, and the drying time is 12-48 h; through drying before the intensification carbonization to guarantee that the raw materials water content is less than 20% to avoid carbonization process living beings schizolysis can produce tar, take place the production of burning phenomenon under the high condition of woody plant raw materials water content.
Preferably, the elevated temperature carbonization and the elevated temperature activation are both performed in a protective atmosphere including at least one of argon, nitrogen, helium, and neon.
Preferably, the temperature-increasing carbonization conditions include: heating to 400-600 ℃ at a heating rate of 1-10 ℃/min, preserving heat at 400-600 ℃ for 1-5 h, and finally cooling to room temperature along with the furnace.
It should be noted that the biomass initially forms a porous char structure during the carbonization process, and most of the non-char components are separated from the char by the cracking reaction to form a gas purge, and the pore framework of the char is initially formed during the carbonization process.
The activator comprises potassium hydroxide (KOH), sodium hydroxide (NaOH), lithium hydroxide (LiOH), and sodium bicarbonate (NaHCO)3) Potassium bicarbonate (KHCO)3)Lithium carbonate (Li)2CO3) Sodium carbonate (Na)2CO3) Potassium carbonate (K)2CO3) Ferrous chloride (FeCl)2) Iron chloride (FeCl)3) Copper chloride (CuCl)2) Cobalt chloride (CoCl)3) Zinc chloride (ZnCl)2) Phosphoric acid (H)3PO4) Potassium dihydrogen phosphate (KH)2PO4) Potassium hydrogen sulfate (KHSO)4) Sodium hydrogen sulfate (NaHSO)4) Calcium hydroxide (Ca (OH)2) Phosphorus pentoxide (P)2O5) And zinc trifluoromethanesulfonate (Zn (CF)3SO3)2) At least one of (1).
The mass ratio of the activated coarse carbon material to the activating agent is (1-1.5): (1-4).
Preferably, the conditions for activation at elevated temperature include: heating to 800-1000 ℃ at a heating rate of 1-10 ℃/min, preserving heat at 800-1000 ℃ for 1-5 h, and finally cooling to room temperature along with the furnace.
It should be noted that the activation process is that unsaturated carbon atoms or active sites exposed on the surface of the crystallites react with the activation gas and other molecules; the microcrystal surface is a high-activity site area on the surface of the carbonized active coarse carbon material, and the activated gas refers to CO generated by decomposition of oxygen-containing functional groups and sulfur-containing functional groups in the activation process2And SO2When the gas is inThe carbon continuously generates a cyclic activation reaction, and other molecules refer to added activator molecules; new pores are continuously formed by the uneven combustion of the surfaces of the microcrystals, and the activated carbon material is obtained.
In the temperature rise rate, the temperature rise and the heat preservation time range in the carbonization and activation processes, the structure and the activity of the material are not destructively influenced while the activation effect is ensured.
Further, the preparation method of the activated carbon material further comprises the following steps: acid washing is carried out on the activated carbon material obtained by heating and activating; preferably, the pickling process comprises: stirring and mixing the activated carbon material and an acid solution, wherein the stirring speed is preferably 500-1200 r/min, and the stirring time is 0.5-2 h; then carrying out solid-liquid separation; and removing impurities such as metal ions on the surface of the activated carbon material by acid washing.
Preferably, the volume ratio of the acid solution to the activated carbon material is (150-300): (1-10); the acid solution comprises at least one of hydrochloric acid solution, sulfuric acid solution, nitric acid solution, acetic acid solution, perchloric acid solution, hypochlorous acid solution and hydrofluoric acid solution with the concentration of 0.1-1M, and impurities such as metal ions on the surface of the activated carbon material can be well dissolved in the acid solution to be removed.
More preferably, the hydrochloric acid solution with the concentration of 0.5-1 mol/L and the activated carbon material are mixed according to the volume ratio (200-300): (2-8), and stirring at a stirring speed of 600-1000 r/min for 60-120 min.
The solid-liquid separation may be at least one of filtration and centrifugal separation.
The filtration is preferably performed by using qualitative filter paper with the pore diameter of 20-60 μm.
Further, the pickling step further comprises water washing, the pickling step can be carried out directly by using water, or the water and the pickled activated carbon material are stirred and mixed and then subjected to solid-liquid separation to wash away residual acid, and the pH value of the final washing liquid is 6.5-7.5 by using the water washing step.
Further, the washing step further comprises drying, optionally, the drying temperature is 60-100 ℃, and the drying time is 1-24 hours.
The invention also provides a composite material containing the activated carbon material.
Further, the composite material also comprises a metal material, wherein the metal material comprises at least one of a metal simple substance and a metal compound; the metal elementary substance comprises at least one of V (alum), Fe (iron), Co (cobalt), Mn (manganese), Mo (molybdenum), Ni (nickel), Cu (copper) and Ag (silver); the metal compound comprises an oxide and/or sulfide of at least one of V (vanadium), Fe (iron), Co (cobalt), Mn (manganese), Mo (molybdenum), Ni (nickel), Cu (copper) and Ag (silver); the particle size of the metal material is preferably 5 to 500 nm.
Preferably, the mass ratio of the activated carbon material to the metal material is (85-95): (5-15).
The invention also provides a preparation method of the composite material, which comprises the following steps: mixing raw materials including the activated carbon material and the metal material.
Further, the preparation method of the composite material also comprises the step of carrying out high-energy ball milling treatment on the mixed mixture; the conditions of the high-energy ball milling treatment comprise: the mass ratio of the mixture to the grinding balls is (1-1.5): (100-200), the ball milling speed is 600-1200 r/min, and the ball milling time is 0.5-2 h; the grinding balls preferably adopt grinding balls with the diameter of 1-5 mm and grinding balls with the diameter of 8-10 mm, and the ratio of the total volume of the grinding balls with the diameter of 1-5 mm to the total volume of the grinding balls with the diameter of 8-10 mm is (1-15): (25-50), zirconium balls are preferably used as the grinding balls.
The invention also provides a cathode material of a zinc ion energy storage device, which comprises the composite material, wherein the composite material is used as an active substance in the cathode material of the zinc ion energy storage device.
Further, the cathode material also comprises a conductive agent and a binder; the conductive agent and the binder can be enumerated by conductive agent materials and binder materials which are commonly used in cathode materials of zinc ion energy storage devices at present.
Preferably, the mass ratio of the composite material to the conductive agent to the binder is (8-9.5): (1-0.2): (1-0.3).
The invention also provides a preparation method of the cathode material of the zinc ion energy storage device, which comprises the following steps: and uniformly mixing the raw materials including the composite material, the conductive agent and the binder.
The invention also provides a cathode plate of the zinc ion energy storage device, which comprises a current collector and a cathode material layer, wherein the cathode material layer is prepared by coating the cathode material of the zinc ion energy storage device on the current collector.
Preferably, the cathode sheet has a thickness of 40 to 210 μm and an area density of 1 to 5mg/cm2(ii) a The thickness of the cathode material layer is 50 to 200 μm.
Preferably, the current collector is made of stainless steel, and the thickness of the current collector is 50-200 μm.
The invention also provides a preparation method of the cathode plate of the zinc ion energy storage device, which comprises the following steps:
providing a current collector;
and coating the cathode material on a current collector, and drying to obtain the cathode material layer.
Preferably, the coating thickness is 50-200 μm; the drying comprises pre-drying and post-drying; optionally, the pre-drying temperature is 80-120 ℃, and the time is 20-40 min; the temperature of the post-drying is 80-120 ℃, and the time is 12-48 h.
Preferably, the method further comprises the following steps after the pre-drying and before the post-drying: rolling the pre-dried product; the rolling temperature is 100-200 ℃.
The invention also provides a zinc ion energy storage device which comprises the cathode plate.
Furthermore, the zinc ion energy storage device also comprises an anode sheet and electrolyte; the anode sheet is preferably a zinc foil sheet.
The electrolyte is an aqueous solution containing zinc ions; optionally, the electrolyte of the electrolyte is zinc chloride (ZnCl)2) Zinc sulfate heptahydrate (ZnSO)4·7H2O), zinc nitrate hexahydrate (Zn (NO)3)2·6H2O), zinc acetate (Zn (CH)3COO)2) Zinc perchlorate hexahydrate (Zn (ClO)4)2·6H2O), zinc trifluoromethanesulfonate (Zn (CF)3SO3)2) Zinc citrate (Zn)3(C6H5O7)2·2H2O), zinc oxalate (ZnC)2O4·2H2O), zinc borofluoride (Zn (BF)4)2) Zinc dihydrogen phosphate (Zn (H)2PO4)2) Zinc bromide (ZnBr)2) And zinc iodide (ZnI)2) At least one of a salt; preferably, the concentration of the electrolyte is 0.5-3M; and the conductivity of the electrolyte at 25 ℃ is 10.00-30.00 mS/cm.
Preferably, the zinc ion energy storage device is a CR2015 button cell battery, a CR2025 button cell battery, a CR2032 button cell battery or an electrode area of 2-10 cm2The aluminum plastic film soft package battery.
The invention can limit the metal material in the hierarchical pore structure of the active carbon material well by compounding the active carbon material with a reasonable hierarchical pore structure with the metal material, the hierarchical pore structure provides a large amount of matching space sites for the metal material, the structural stability of the composite material is effectively improved, the electrical conductivity of the active carbon material is improved by the excellent electrical conductivity of the metal material, the composite material obtained by compounding the metal material with the active carbon material of the invention is applied to the cathode of a zinc ion energy storage device, the unsolvated electrolyte anions can be rapidly adsorbed, the volume change generated in the alloying reaction process of the metal material in the composite material and zinc ions is well inhibited, the dissolution of the metal material is also well inhibited, the capacitance performance of the zinc ion energy storage device is stimulated to the maximum extent, so that the zinc ion energy storage device has high capacity and good cycle stability, the specific capacity of the zinc ion energy storage device can reach 100-150 mAh/g, excellent electrochemical energy storage performance is shown, and the zinc ion energy storage device has a potential wide application prospect in the field of electrochemical energy storage, is low in preparation cost, simple and easy to implement, high in yield and suitable for large-scale industrial production.
Embodiments of the present invention will be described in detail below with reference to specific examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present 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.
Example 1
(1) The persimmon branches are mechanically crushed into powder of 300 meshes in a crusher at a high speed of 35000r/min, then the powder is placed in a tube furnace, the temperature is raised to 600 ℃ at a speed of 5 ℃/min under the protection of nitrogen, the temperature is kept for 2h, and finally the powder is cooled to room temperature along with the furnace to obtain the active coarse carbon material.
(2) Mixing the activated crude carbon material obtained in the step (1) with KOH according to the mass ratio of 1: 4, mixing, placing in a tube furnace, heating to 850 ℃ at the speed of 5 ℃/min under the protection of nitrogen, preserving heat for 2h, and finally cooling to room temperature along with the furnace.
(3) Mixing the activated carbon material obtained in the step (2) and a 1M hydrochloric acid solution according to a volume ratio of 7: 150, stirring for 120min at the speed of 900r/min, filtering (adopting qualitative filter paper with the particle size of 60 mu m), performing suction filtration and washing on the solid obtained by filtering by using deionized water until the pH value of the filtrate is 6.8, collecting the solid material after suction filtration, and drying in an oven at the temperature of 100 ℃ for 18 h.
(4) Mixing the activated carbon material obtained in the step (3) with a copper material with the granularity of 5-10 nm according to a mass ratio of 90: 10, placing the mixed mixture into a high-energy ball mill for treatment, wherein the mass ratio of the mixed mixture to grinding balls is 1.2: 180, the grinding balls adopt zirconium balls with the diameter of 1-5 mm and zirconium balls with the diameter of 8-10 mm, and the ratio of the total volume of the zirconium balls with the diameter of 1-5 mm to the total volume of the zirconium balls with the diameter of 8-10 mm is 1: 25, the ball milling speed is 800r/min, and the ball milling time is 1.5h, so as to obtain the composite material.
(5) And (3) mixing the composite material obtained in the step (5), Super-P and polyvinylidene fluoride according to the mass ratio of 8.5: 0.7: 0.8, evenly mixing to prepare slurry, coating the slurry on a stainless steel foil with the thickness of 10 mu m to be 110 mu m, then pre-drying for 40min at the temperature of 80 ℃ to obtain a prefabricated pole piece, and pressing the prefabricated pole piece to be 90 mu m by using a roller press under the condition that the rolling temperature is 150 ℃ and the surface density is 2.0mg/cm2Finally drying in an oven at 100 ℃ for 24 hours to prepare zinc ionsAnd the cathode plate of the sub energy storage device.
(6) Zn (CF)3SO3)2Dissolving in deionized water to prepare 2M Zn (CF)3SO3)2And (3) using an aqueous solution as an electrolyte (the conductivity of the electrolyte is 21.00mS/cm at 25 ℃), using the cathode sheet obtained in the step (5) as a cathode, using a zinc foil with the thickness of 30 mu m and the purity of 99% as an anode, and using Whatman 1823-.
Example 2
(1) The persimmon branches are mechanically crushed into 200-mesh powder at a high speed in a crusher of 30000r/min, then the powder is placed in a tube furnace, the temperature is raised to 400 ℃ at a speed of 1 ℃/min under the protection of nitrogen, the temperature is kept for 5h, and finally the powder is cooled to room temperature along with the furnace to obtain the active coarse carbon material.
(2) Mixing the active crude carbon material obtained in the step (1) with NaHCO3According to the mass ratio of 1: 1, placing the mixture in a tube furnace, heating the mixture to 800 ℃ at the speed of 1 ℃/min under the protection of nitrogen, preserving the heat for 5 hours, and finally cooling the mixture to room temperature along with the furnace.
(3) Mixing the activated carbon material obtained in the step (2) and 0.5M hydrochloric acid solution according to the volume ratio of 1: 150, stirring for 60min at the speed of 1000r/min, filtering (adopting qualitative filter paper of 40 mu m), performing suction filtration and washing on the solid obtained by filtering by using deionized water until the pH value of the filtrate is 7.5, collecting the solid material after suction filtration, and drying in an oven at 80 ℃ for 15 h.
(4) Mixing the activated carbon material obtained in the step (3) with a copper material with the granularity of 5-10 nm according to a mass ratio of 85: 15, placing the mixed mixture in a high-energy ball mill for treatment, wherein the mass ratio of the mixed mixture to grinding balls is 1: 100, the grinding balls adopt zirconium balls with the diameter of 1-5 mm and zirconium balls with the diameter of 8-10 mm, and the ratio of the total volume of the zirconium balls with the diameter of 1-5 mm to the total volume of the zirconium balls with the diameter of 8-10 mm is 8: and 40, ball milling speed is 6800r/min, and ball milling time is 2h, so that the composite material is obtained.
(5) And (3) mixing the composite material obtained in the step (5), Super-P and polyvinylidene fluoride according to the mass ratio of 8: 1: 1 mixing uniformly to prepareCoating the slurry on a stainless steel foil with the thickness of 60 mu m, pre-drying at 120 ℃ for 20min to obtain a prefabricated pole piece, and pressing the prefabricated pole piece to 40 mu m by using a roller press at the rolling temperature of 100 ℃ and the surface density of 5mg/cm2And finally, drying in an oven at 120 ℃ for 15h to prepare the cathode sheet of the zinc ion energy storage device.
(6) Zn (CF)3SO3)2Dissolving in deionized water to prepare 0.5M Zn (CH)3COO)2And (3) using an aqueous solution as an electrolyte (the conductivity of the electrolyte is 12.00mS/cm at 25 ℃), using the cathode sheet obtained in the step (5) as a cathode, using a zinc foil with the thickness of 30 mu m and the purity of 99% as an anode, and using Whatman 1823-.
Example 3
(1) The poplar branches are mechanically crushed into 250-mesh powder at a high speed in a crusher at 32000r/min, then the powder is placed in a tube furnace, the temperature is raised to 600 ℃ at a speed of 10 ℃/min under the protection of nitrogen, the temperature is kept for 1h, and finally the powder is cooled to room temperature along with the furnace to obtain the active coarse carbon material.
(2) Mixing the active coarse carbon material obtained in the step (1) with Li2CO3According to the mass ratio of 1.5: 2.7, placing the mixture in a tube furnace, heating the mixture to 100 ℃ at the speed of 10 ℃/min under the protection of nitrogen, preserving the heat for 1h, and finally cooling the mixture to room temperature along with the furnace.
(3) Mixing the activated carbon obtained in the step (2) and a 0.5M nitric acid solution according to a volume ratio of 1: 300, stirring at 1200r/min for 4min, filtering (using 20 μm qualitative filter paper), suction-filtering and washing the solid obtained by filtering with deionized water until the pH of the filtrate is 6.5, collecting the solid material after suction-filtering, and drying in an oven at 60 ℃ for 24 h.
(4) Mixing the activated carbon material obtained in the step (3) with a copper material with the granularity of 10-50 nm according to a mass ratio of 95: 5, placing the mixed mixture into a high-energy ball mill for treatment, wherein the mass ratio of the mixed mixture to grinding balls is 1.5: 200, grinding balls adopt zirconium balls with the diameter of 1-5 mm and zirconium balls with the diameter of 8-10 mm, and the ratio of the total volume of the zirconium balls with the diameter of 1-5 mm to the total volume of the zirconium balls with the diameter of 8-10 mm is 15: 50, ball milling speed of 1200r/min, ball milling time of 0.5h, and obtaining the composite material.
(5) And (3) mixing the composite material obtained in the step (5), Super-P and polyvinylidene fluoride according to the mass ratio of 9.5: 0.2: 0.3, evenly mixing to prepare slurry, coating the slurry on a stainless steel foil with the thickness of 200 mu m, pre-drying for 30min at the temperature of 100 ℃ to obtain a prefabricated pole piece, and pressing the prefabricated pole piece to the thickness of 180 mu m by using a roller press under the condition that the rolling temperature is 200 ℃ and the surface density is 1.0mg/cm2And finally drying in an oven at 120 ℃ for 12h to prepare the cathode sheet of the zinc ion energy storage device.
(6) Zn (BF) is reacted4)2Dissolving in deionized water to prepare 1M Zn (BF)4)2And (3) using an aqueous solution as an electrolyte (the conductivity of the electrolyte is 30.00mS/cm at 25 ℃), using the cathode sheet obtained in the step (5) as a cathode, using a zinc foil with the thickness of 30 mu m and the purity of 99% as an anode, and using Whatman 1823-.
Example 4
This example 4 differs from example 1 in that: step (4): the copper material was replaced with a copper oxide material, otherwise the same as in example 1.
Example 5
This example 5 differs from example 1 in that: step (4): the copper material was replaced with copper sulfide material, otherwise the same as in example 1.
Comparative example 1
This comparative example 1 differs from example 1 in that: step (1): heating to 600 ℃ at the speed of 10 ℃/min, then preserving heat for 1h, and replacing heating to 550 ℃ at the speed of 15 ℃/min, and then preserving heat for 1.5 h; step (2): heating to 850 ℃ at the speed of 5 ℃/min, preserving heat for 2h, replacing heating to 800 ℃ at the speed of 15 ℃/min, and preserving heat for 1.5 h; step (3): the volume ratio of the activated carbon material to the 1M hydrochloric acid solution is 7: 150 is replaced by 9: 140 of a solvent; otherwise, the same procedure as in example 1 was repeated.
Comparative example 2
This comparative example 2 differs from example 1 in that: step (1): heating to 600 ℃ at the speed of 10 ℃/min, then preserving heat for 1h, and replacing heating to 550 ℃ at the speed of 0.8 ℃/min, and then preserving heat for 1.5 h; step (2): heating to 850 ℃ at the speed of 5 ℃/min, preserving heat for 2h, replacing heating to 800 ℃ at the speed of 0.8 ℃/min, and preserving heat for 1.5 h; step (3): the volume ratio of the activated carbon material to the 1M hydrochloric acid solution is 7: 150 is replaced by 9: 120 of a solvent; otherwise, the same procedure as in example 1 was repeated.
Comparative example 3
This comparative example 3 differs from example 1 in that: step (1): replacing persimmon branches with wheat straws; otherwise, the same procedure as in example 1 was repeated.
Comparative example 4
This comparative example 4 differs from example 1 in that: step (1): replacing the persimmon branches with corncobs; otherwise, the same procedure as in example 1 was repeated.
Comparative example 5
This comparative example 5 differs from example 1 in that: removing the step (4), and replacing the composite material in the step (5) with the activated carbon material obtained in the step (3); otherwise, the same procedure as in example 1 was repeated.
Comparative example 6
This comparative example 6 differs from example 1 in that: step (4): replacing the copper material with the granularity of 5-10 nm with the copper material with the granularity of 800-1000 nm; otherwise, the same procedure as in example 1 was repeated.
Comparative example 7
This comparative example 7 differs from example 1 in that: step (4): the mass ratio of the activated carbon material to the copper material is 90: 10 is replaced by 80: 20; otherwise, the same procedure as in example 1 was repeated.
The performance results of the activated carbon materials obtained in the above examples 1 to 3 and comparative examples 1 to 4, which were prepared through the steps (1) to (3), are shown in the following table 1.
TABLE 1
Figure BDA0002803501810000191
Figure BDA0002803501810000201
FIG. 1 shows the SEM topography of the activated carbon material prepared in example 1 of the present invention; FIG. 2 is a graph showing isothermal nitrogen adsorption and desorption curves of the activated carbon material prepared in example 1 of the present invention; FIG. 3 is a BET plot of the activated carbon material prepared in example 1 of the present invention. As can be seen from the SEM morphology in fig. 1, the activated carbon material prepared in example 1 of the present invention has a rich pore structure; while the nitrogen adsorption and desorption isotherm curve of FIG. 2 is shown at p/p0The sharp rise near 0 indicates that the activated carbon material prepared in the example 1 of the invention has rich micropores, and p/p0The receipt ring around 0.5 indicates that the activated carbon material prepared in example 1 of the invention has abundant mesopores.
From the results of table 1 above, it can be seen that: the specific surface area of the activated carbon material prepared by the embodiment of the invention is 1800-2600 m2(ii)/g; the total volume of the pores of the activated carbon material is 1.10-1.70 cm3The volume of micropores with the pore diameter of less than 1nm accounts for 1-13% of the total volume of the pores, the volume of mesopores with the pore diameter of 1-10 nm accounts for 48-58% of the total volume of the pores, and the volume of macropores with the pore diameter of more than 10nm accounts for 29-41% of the total volume of the pores.
The electrochemical performance results of the zinc ion energy storage devices prepared in the above examples 1 to 5 and comparative examples 1 to 7 are shown in table 2 below.
TABLE 2
Figure BDA0002803501810000211
FIG. 4 is a CV diagram of the zinc ion energy storage devices prepared in example 1 and comparative example 5 of the present invention at a scan rate of 1 mV/s; FIG. 5 is a graph showing CV curves of the zinc ion energy storage device prepared in example 1 of the present invention at different scan rates of 1mV/s, 5mV/s, 10mV/s and 20 mV/s; FIG. 6 shows CV graphs of the zinc ion energy storage device prepared in comparative example 5 at different scan rates of 1mV/s, 5mV/s, 10mV/s and 20mV/s, and it can be seen that the cycling performance of the zinc ion energy storage device prepared in example 1 of the present invention is significantly better than that of the zinc ion energy storage device prepared in comparative example 5.
From the results of table 2 above and fig. 4 to 6, it can be seen that: the zinc ion energy storage device prepared by the invention has high capacity, excellent cycle performance and good rate performance.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features included in other embodiments, rather than other features, combinations of features of different embodiments are meant to be within the scope of the invention and form different embodiments. For example, in the claims above, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.

Claims (10)

1. The activated carbon material is characterized in that the specific surface area of the activated carbon material is 1800-2600 m2(ii)/g; the total volume of the pores of the activated carbon material is 1.10-1.70 cm3The volume of micropores with the pore diameter of less than 1nm accounts for 1-13% of the total volume of the pores, the volume of mesopores with the pore diameter of 1-10 nm accounts for 48-58% of the total volume of the pores, and the volume of macropores with the pore diameter of more than 10nm accounts for 29-41% of the total volume of the pores.
2. The activated carbon material of claim 1, further comprising at least one heteroatom of O, F, N, P, S;
preferably, the activated carbon material comprises the following element components in percentage by mass based on 100% of the total mass of the activated carbon material: 78-95% of C element, 5-13% of O element, 0-3% of F element, 0-2% of N element, 0-2.5% of P element and 0-1.5% of S element.
3. A method for producing an activated carbon material according to claim 1 or 2, comprising:
providing woody plant powder;
heating and carbonizing the woody plant powder in a protective atmosphere or a vacuum environment to obtain an active crude carbon material;
and mixing the active coarse carbon material with an activating agent, and heating and activating in a protective atmosphere or a vacuum environment to obtain the active carbon material.
4. The method for preparing an activated carbon material according to claim 3, wherein the woody plant powder is pulverized by a pulverizer with a rotating speed of 30000-35000 r/min;
preferably, the particle size of the woody plant powder is 50-300 meshes;
preferably, the woody plant comprises roots and/or stems of at least one of poplar, phoenix tree, pine, persimmon tree, willow, walnut tree, pomegranate tree and wintergreen;
preferably, the method further comprises, before the temperature-rising carbonization: drying the crushed woody plant;
preferably, the drying temperature is 80-150 ℃, and the drying time is 12-48 h;
preferably, the temperature-rising carbonization and the temperature-rising activation are both carried out in a protective atmosphere environment;
preferably, the protective atmosphere comprises at least one of argon, nitrogen, helium and neon;
preferably, the temperature-rising carbonization conditions include: heating to 400-600 ℃ at a heating rate of 1-10 ℃/min, and preserving heat for 1-5 h at 400-600 ℃;
preferably, the activator includes at least one of potassium hydroxide, sodium hydroxide, lithium hydroxide, sodium bicarbonate, potassium bicarbonate, lithium carbonate, sodium carbonate, potassium carbonate, ferrous chloride, ferric chloride, cupric chloride, cobalt chloride, zinc chloride, phosphoric acid, potassium dihydrogen phosphate, potassium hydrogen sulfate, sodium bisulfate, calcium hydroxide, phosphorus pentoxide, and zinc trifluoromethanesulfonate;
preferably, the mass ratio of the activated crude carbon material to the activating agent is (1-1.5): (1-2);
preferably, the temperature-rising activation conditions include: heating to 800-1000 ℃ at a heating rate of 1-10 ℃/min, and preserving heat for 1-5 h at 800-1000 ℃.
5. The method of preparing an activated carbon material of claim 3, further comprising: carrying out acid washing on the activated carbon material obtained by heating and activating;
preferably, the pickling process comprises: mixing the activated carbon material with an acid solution, and then carrying out solid-liquid separation;
preferably, the volume ratio of the acid solution to the activated carbon material is (150-300): (1-10);
preferably, the acid solution comprises at least one of hydrochloric acid solution, sulfuric acid solution, nitric acid solution, acetic acid solution, perchloric acid solution, hypochlorous acid solution and hydrofluoric acid solution with the concentration of 0.1-1M;
optionally, the mixing mode adopts stirring mixing; preferably, the stirring speed is 500-1200 r/min, and the stirring time is 0.5-2 h;
preferably, the solid-liquid separation comprises at least one of filtration and centrifugation;
preferably, qualitative filter paper with the pore diameter of 20-60 mu m is adopted for filtering;
preferably, the acid washing process further comprises the following steps: washing the activated carbon material after acid washing with water;
preferably, the method further comprises the following steps after water washing: drying the washed activated carbon material; optionally, drying the washed activated carbon material at 60-100 ℃ for 1-24 h.
6. A composite material comprising the activated carbon material of claim 1 or 2;
preferably, the composite material further comprises a metal material, and the metal material comprises at least one of a metal simple substance and a metal compound;
preferably, the metal simple substance comprises at least one of V, Fe, Co, Mn, Mo, Ni, Cu and Ag; the metal compound comprises an oxide and/or sulfide of at least one of V, Fe, Co, Mn, Mo, Ni, Cu and Ag;
preferably, the particle size of the metal material is 5-500 nm;
preferably, the mass ratio of the activated carbon material to the metal material is (85-95): (5-15).
7. A method of making the composite material of claim 6, comprising: mixing raw materials including the activated carbon material and the metal material;
preferably, the method further comprises the step of carrying out high-energy ball milling treatment on the mixed mixture;
preferably, the conditions of the high-energy ball milling treatment include: the mass ratio of the mixture to the grinding balls is (1-1.5): (100-200), the ball milling speed is 600-1200 r/min, and the ball milling time is 0.5-2 h;
preferably; the grinding balls are grinding balls with the diameter of 1-5 mm and grinding balls with the diameter of 8-10 mm, and the ratio of the total volume of the grinding balls with the diameter of 1-5 mm to the total volume of the grinding balls with the diameter of 8-10 mm is (1-15): (25-50).
8. A cathode material for a zinc ion energy storage device comprising the composite material of claim 6.
9. A cathode sheet of a zinc ion energy storage device, characterized by comprising the cathode material of the zinc ion energy storage device of claim 8.
10. A zinc ion energy storage device comprising the cathode sheet of claim 9;
preferably, the zinc ion energy storage device further comprises an anode sheet and electrolyte;
preferably, the anode sheet is a zinc foil sheet;
preferably, the electrolyte is an aqueous solution containing zinc ions;
optionally, the electrolyte of the electrolyte is at least one of zinc chloride, zinc sulfate heptahydrate, zinc nitrate hexahydrate, zinc acetate, zinc perchlorate hexahydrate, zinc trifluoromethanesulfonate, zinc citrate, zinc oxalate, zinc borofluoride, zinc dihydrogen phosphate, zinc bromide and zinc iodide;
preferably, the concentration of the electrolyte is 0.5-3M;
preferably, the conductivity of the electrolyte at 25 ℃ is 10.00-30.00 mS/cm.
CN202011359254.4A 2020-11-27 2020-11-27 Activated carbon material, composite material, cathode material and cathode sheet of zinc ion energy storage device and zinc ion energy storage device Pending CN112467109A (en)

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