CN112357921B - Hierarchical porous carbon, and preparation method and application thereof - Google Patents

Hierarchical porous carbon, and preparation method and application thereof Download PDF

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CN112357921B
CN112357921B CN202011324472.4A CN202011324472A CN112357921B CN 112357921 B CN112357921 B CN 112357921B CN 202011324472 A CN202011324472 A CN 202011324472A CN 112357921 B CN112357921 B CN 112357921B
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porous carbon
hierarchical porous
application example
petroleum asphalt
weight loss
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CN112357921A (en
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胡涵
晁会霞
刘昭斌
邢涛
杨浩
刘海燕
牛国瑞
韩嘉
李智
张奎同
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Yankuang Group Corp Ltd
China University of Petroleum East China
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Yankuang Group Corp Ltd
China University of Petroleum East China
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C01B32/312—Preparation
    • C01B32/318—Preparation characterised by the starting materials
    • C01B32/33—Preparation characterised by the starting materials from distillation residues of coal or petroleum; from petroleum acid sludge
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/44—Raw materials therefor, e.g. resins or coal
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
    • 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
    • Y02E60/13—Energy storage using capacitors

Abstract

The invention discloses a hierarchical porous carbon, a preparation method and application thereof; the preparation method of the hierarchical porous carbon comprises the following steps: (1) mixing petroleum asphalt with bicarbonate to obtain a mixture; (2) calcining the mixture obtained in the step (1) in a protective atmosphere, and cooling to room temperature after calcination to obtain a calcined material; (3) washing the calcined material obtained in the step (2) with water, and drying to obtain the hierarchical porous carbon; the hierarchical porous carbon uses hard petroleum asphalt and bicarbonate as raw materials, and the raw materials are wide in source and low in price; the bicarbonate has extremely low equipment corrosivity, and an acid reagent is not required to be introduced to remove a template and an activating agent, so that the industrial production flow and energy consumption are greatly reduced; when the hierarchical porous carbon is used for anode and cathode materials, the hierarchical porous carbon has good circulation stability and ideal coulombic efficiency, and has good application prospects.

Description

Hierarchical porous carbon, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of energy storage, relates to an energy storage material, and particularly relates to hierarchical porous carbon and a preparation method and application thereof.
Background
With the rapid development of science and technology and the rapid consumption of non-renewable energy, people have increasingly demanded new electrochemical energy storage devices for storing and converting renewable energy. So far, the common energy storage systems on the market mainly comprise lithium ion batteries and super capacitors. Lithium ion batteries have high energy density, and are widely used in the fields of mobile phones, computers, electric vehicles and the like, but have the defect of poor cycle life. Compared with a lithium ion battery, the super capacitor has ultrahigh power density, is widely applied to the fields of micro devices, sensors and the like, but the development prospect of the super capacitor is greatly limited by the lower energy density. As a novel electrochemical energy storage device, a lithium ion capacitor combining the respective advantages of a lithium ion battery and a supercapacitor has been produced. The lithium ion capacitor consists of a battery-type negative electrode, a capacitance-type positive electrode and a lithium-containing organic electrolyte, has higher energy density and power density, and also has a super-long cycle life and a good application prospect. Up to now, high performance lithium ion capacitors constructed of carbon-based materials have received much attention from researchers due to their good kinetic matching between the positive and negative electrodes.
The electrode material is a main factor determining the performance of the lithium ion capacitor, and the porous carbon material is widely applied to the field of electrochemical energy storage due to excellent physicochemical properties. Up to now, there have been various carbon materials studied and secondarily modified, such as activated carbon, two-dimensional carbon nanosheet, carbon nanofiber, carbon nanoball, carbon nanotube, carbon quantum dot, graphene, and the like. The porous carbon with the hierarchical porous skeleton is widely applied to various electrochemical energy storage devices due to the high specific surface area, rich pore channel structures and good chemical stability (strong acid resistance, strong alkali resistance and high temperature resistance). At present, raw materials for industrially preparing the carbon-based material mainly come from biomacromolecules (including straws, peanut shells, coconut shells, rice husks and the like) and heavy oil macromolecules (including petroleum asphalt, coal asphalt and the like), wherein the petroleum asphalt becomes a carbon-based material precursor with great potential due to the unique advantages of high carbon content and low price.
Therefore, raw materials for preparing the porous carbon with the hierarchical porous skeleton mainly comprise organic and biological macromolecules such as glucose, sucrose and waste plant shells and heavy oil-based macromolecules, and the preparation method mainly comprises a hard template method, a soft template method and a high-temperature strong-base activation method. Because the hard template needs to be removed by adding an acid reagent, the production process is complicated, a large amount of acid reagent is consumed, the price is high, and the development concept of green environmental protection is not met. The soft template has higher cost, and although the template is not required to be removed by an additional reagent, the requirements on raw materials and the template are strict, so that the industrial mass production cannot be basically realized. Although the process for preparing the porous carbon by directly activating the strong base is simple, the requirement on equipment is high, the strong base has high corrosivity, an acid reagent needs to be introduced to remove an activating agent, the operation is complex, and the production operation cost is further increased.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide the hierarchical porous carbon and the preparation method and the application thereof, the hierarchical porous carbon has wide sources of preparation raw materials and small corrosivity to equipment, the flow and the cost of industrial production are greatly reduced, and the prepared hierarchical porous carbon can provide good cycle performance, energy density and power density when being used as an electrode active substance for a metal ion capacitor, a secondary battery and an electric device, and has good application prospect.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing hierarchical porous carbon, comprising the steps of:
(1) uniformly mixing petroleum asphalt and bicarbonate to obtain a mixture;
(2) calcining the mixture obtained in the step (1) in a protective atmosphere, and cooling to room temperature after calcination to obtain a calcined material;
(3) and (3) washing the calcined material obtained in the step (2) with water, and drying to obtain the hierarchical porous carbon.
The room temperature in the present invention is 15 to 30 ℃ and may be, for example, 15 ℃, 18 ℃, 20 ℃, 21 ℃, 24 ℃, 27 ℃, 28 ℃ or 30 ℃, but is not limited to the values listed, and other values not listed in the range of values are equally applicable.
The petroleum asphalt is preferably hard petroleum asphalt which is a byproduct in the petroleum refining process, and compared with a conventional activated carbon material, the hard petroleum asphalt has the advantages of low price and wide source, and the high carbon content of the hard petroleum asphalt enables the yield of the prepared hierarchical porous carbon to be higher.
The bicarbonate has extremely low equipment corrosivity, does not need to introduce an acidic reagent to remove a template and an activating agent, and greatly reduces the industrial production flow and energy consumption.
According to the invention, the hierarchical porous carbon is prepared by taking the petroleum asphalt and the bicarbonate as raw materials, so that the raw material sources are expanded, the requirement of the preparation process on equipment is low, secondary pollution to the environment is avoided, and the cost of industrial production of the hierarchical porous carbon is reduced. The hierarchical porous carbon prepared by the preparation method has rich three-dimensional pore channel structures, can shorten the diffusion path of lithium ions, reduce the diffusion impedance of the lithium ions, provide rich space for the storage of the lithium ions, contribute to providing rich active sites for the storage of the lithium ions, greatly improve the lithium storage capacity of the material, and increase the capacitance contribution ratio of the capacity of the material.
Preferably, the petroleum asphalt in the step (1) is hard petroleum asphalt;
preferably, the initial weight loss temperature of the hard petroleum asphalt is more than or equal to 300 ℃, the weight loss between 300 and 635 ℃ is more than or equal to 75 wt%, and the temperature of 95 wt% weight loss is more than or equal to 800 ℃.
The initial weight loss temperature of the hard petroleum asphalt of the present invention is not less than 300 deg.C, and may be, for example, 300 deg.C, 310 deg.C, 320 deg.C, 330 deg.C, 340 deg.C, 350 deg.C, 360 deg.C, 370 deg.C, 380 deg.C, 390 deg.C or 400 deg.C, but is not limited to the values listed, and other values not listed in the range of values are also applicable.
The weight loss of the hard petroleum asphalt between 300 ℃ and 635 ℃ is more than or equal to 75 wt%, and can be, for example, 75 wt%, 76 wt%, 77 wt%, 78 wt%, 79 wt%, 80 wt%, 81 wt%, 82 wt%, 83 wt%, 84 wt% or 85 wt%, but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
The hard petroleum asphalt has a 95 wt% weight loss temperature of 800 deg.C or more, such as 800 deg.C, 810 deg.C, 820 deg.C, 830 deg.C, 840 deg.C or 850 deg.C, but not limited to the recited values, and other unrecited values within the range of values are equally applicable.
Preferably, the bicarbonate in step (1) is potassium bicarbonate.
The bicarbonate is used as a template agent and an activating agent, and the carbonate generated after calcination can be directly removed by water, so that the removal process is green and pollution-free, and the production cost is effectively reduced; and the bicarbonate has extremely low equipment corrosivity, and an acid reagent is not required to be introduced to remove the template and the active agent in the later period, so that the industrial production flow and the energy consumption are greatly reduced.
Preferably, the mixing of step (1) is a milling mixing.
Preferably, the milling mixing comprises hand milling or dry ball milling.
Preferably, the mass ratio of the petroleum asphalt to the bicarbonate in the step (1) is 1 (3-5), and may be, for example, 1:3, 1:3.5, 1:4, 1:4.5 or 1:5, but is not limited to the enumerated values, and other unrecited values in the numerical range are also applicable.
Preferably, the protective atmosphere of step (2) is a nitrogen atmosphere and/or an inert atmosphere.
The inert atmosphere comprises at least one of argon, neon or helium.
Preferably, the temperature of the calcination in step (2) is 600-800 deg.C, and may be, for example, 600 deg.C, 650 deg.C, 700 deg.C, 750 deg.C or 800 deg.C, but is not limited to the recited values, and other values not recited in the range of values are equally applicable. When the calcination temperature is lower than 600 ℃, the calcination effect cannot be achieved, and when the calcination temperature is higher than 800 ℃, the phenomenon that three-dimensional pore canals collapse seriously exists.
Preferably, the temperature increase rate of the calcination in step (2) is 3-6 deg.C/min, such as 3 deg.C/min, 3.5 deg.C/min, 4 deg.C/min, 4.5 deg.C/min, 5 deg.C/min, 5.5 deg.C/min or 6 deg.C/min, but not limited to the values recited, and other values not recited in the range of values are equally applicable.
When the temperature rise rate of the calcination is smaller, the required temperature rise time is longer, which is not beneficial to improving the calcination efficiency and controlling the decomposition rate of the bicarbonate and influencing the formation of a three-dimensional pore channel structure; when the temperature increase rate of the calcination is high, the time for temperature increase can be shortened, but there is a defect that the collapse of the three-dimensional pore channels is serious.
Preferably, the calcination time in step (2) is 120-300min, such as 120min, 130min, 140min, 150min, 160min, 170min, 180min, 190min, 200min, 210min, 220min, 230min, 240min, 250min, 260min, 270min, 280min, 290min or 300min, but not limited to the recited values, and other non-recited values in the range of values are also applicable.
In the invention, when the calcination time reaches 120min, the preparation of the hierarchical porous carbon can be realized, but the calcination is carried out within 300min of 120-.
Preferably, the cooling of step (2) is furnace cooling.
Preferably, the end point of the water wash in step (3) is a pH of the water wash of 6.5-7.5, which may be, for example, 6.5, 6.6, 6.7, 6.8, 6.9, 7, 7.1, 7.2, 7.3, 7.4 or 7.5, but is not limited to the recited values, and other values not recited in the numerical ranges are equally applicable.
According to the invention, bicarbonate is used as a template agent and an active agent, carbonate generated by decomposition of the bicarbonate can be removed by washing, and the washing end point can be judged when the washing liquid does not contain the bicarbonate. The method adopts the pH value to judge the washing end point more conveniently, thereby reducing the use of washing liquid and playing a role in reducing energy consumption.
Preferably, the drying temperature in step (3) is 60-70 deg.C, such as 60 deg.C, 62 deg.C, 64 deg.C, 65 deg.C, 66 deg.C, 68 deg.C or 70 deg.C, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the drying time in the step (3) is more than or equal to 12 h.
As a preferable technical scheme of the preparation method, the preparation method comprises the following steps:
(1) grinding and mixing the hard petroleum asphalt and the bicarbonate according to the mass ratio of 1 (3-5) to obtain a uniformly mixed mixture; the initial weight loss temperature of the hard petroleum asphalt is more than or equal to 300 ℃, the weight loss between 300 and 635 ℃ is more than or equal to 75 wt%, and the weight loss temperature of 95 wt% is more than or equal to 800 ℃;
(2) heating to 600-800 ℃ at the heating rate of 3-6 ℃/min under the protective atmosphere, calcining the mixture obtained in the step (1) for 300min, and cooling to room temperature along with the furnace after the calcination is finished to obtain a calcined material;
(3) and (3) washing the calcined material obtained in the step (2) until the pH value of a washing liquid is 6.5-7.5, and drying at 60-70 ℃ for more than 12h to obtain the hierarchical porous carbon.
In a second aspect, the present invention provides a hierarchical porous carbon prepared by the preparation method according to the first aspect.
In a third aspect, the present invention provides the use of the hierarchical porous carbon according to the second aspect for a metal-ion capacitor, a secondary battery or an electric device.
The electromotive device includes various functional devices using a metal ion capacitor and/or a secondary battery as a driving power source.
Preferably, the metal ion capacitor is a lithium ion capacitor.
The positive pole piece of the lithium ion capacitor comprises an aluminum foil and an electrode active material coated on the aluminum foil; the negative pole piece of the lithium ion capacitor comprises a copper foil and an electrode active material coated on the copper foil; the electrode active material includes therein the hierarchical porous carbon according to the second aspect.
Preferably, the mass ratio of the positive electrode sheet to the negative electrode sheet is (1-2): 1-2), and can be, for example, 1:1, 1:2 or 2:1, but is not limited to the enumerated values, and other values in the numerical range are also applicable, and preferably 1: 1.
Preferably, the electrode active material includes hierarchical porous carbon, conductive carbon black, and polyvinylidene fluoride.
The mass ratio of the graded porous carbon, the conductive carbon black and the polyvinylidene fluoride includes but is not limited to 8:1: 1.
Preferably, the mass density of the graded porous carbon on the positive pole piece is 0.4-3mg/cm 2 For example, it may be 0.4mg/cm 2 、0.5mg/cm 2 、1mg/cm 2 、1.5mg/cm 2 、2mg/cm 2 、2.5mg/cm 2 Or 3mg/cm 2 But are not limited to the values specified, other values not specified in the range of values are equally applicable, preferably from 0.5 to 1mg/cm 2 。
Preferably, the mass density of the graded porous carbon on the negative pole piece is 0.4-3mg/cm 2 For example, it may be 0.4mg/cm 2 、0.5mg/cm 2 、1mg/cm 2 、1.5mg/cm 2 、2mg/cm 2 、2.5mg/cm 2 Or 3mg/cm 2 But are not limited to the values specified, other values not specified in the range of values are equally applicable, preferably from 0.5 to 1mg/cm 2 。
The recitation of numerical ranges herein includes not only the above-recited numerical values, but also any numerical values between non-recited numerical ranges, and is not intended to be exhaustive or to limit the invention to the precise numerical values encompassed within the range for brevity and clarity.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention uses the petroleum asphalt as the byproduct of the petroleum refining process, compared with the industrial preparation of the activated carbon raw material, the price is low, the source is wide, and the high carbon content leads the yield of the prepared porous carbon product to be higher;
(2) the bicarbonate used in the invention conforms to the development concept of green environmental protection, the potassium carbonate generated in the calcining process can be directly removed by water, and the method is green and pollution-free, effectively reduces the production cost, and has very considerable large-scale application prospect;
(3) the bicarbonate used in the method has extremely low equipment corrosivity, and an acid reagent is not required to be introduced to remove a template and an activating agent, so that the industrial production flow and energy consumption are greatly reduced;
(4) the hierarchical porous carbon can be used as a positive active material and a negative active material of a metal ion capacitor at the same time, and the positive active material and the negative active material comprising the hierarchical porous carbon have good circulation stability, ideal coulombic efficiency and high energy density.
Drawings
FIG. 1(a) is an SEM photograph of the graded porous carbon prepared in example 1;
FIG. 1(b) is an SEM image of the hierarchical porous carbon prepared in example 1;
FIG. 2 is an XRD pattern of the hierarchical porous carbon prepared in example 1;
FIG. 3 is a Raman spectrum of the hierarchical porous carbon prepared in example 1;
FIG. 4(a) is an SEM image of the hierarchical porous carbon prepared in example 2;
FIG. 4(b) is an SEM image of the hierarchical porous carbon prepared in example 2;
FIG. 5 is an XRD pattern of the graded porous carbon prepared in example 2;
FIG. 6 is a Raman spectrum of the hierarchical porous carbon prepared in example 2;
FIG. 7(a) is an SEM image of the hierarchical porous carbon prepared in example 3;
FIG. 7(b) is an SEM image of the hierarchical porous carbon prepared in example 3;
FIG. 8 is an XRD pattern of the hierarchical porous carbon prepared in example 3;
FIG. 9 is a Raman spectrum of the hierarchical porous carbon prepared in example 3;
fig. 10(a) is an SEM image of the hierarchical porous carbon prepared in comparative example 1;
fig. 10(b) is an SEM image of the hierarchical porous carbon prepared in comparative example 1;
fig. 11(a) is an SEM image of the hierarchical porous carbon prepared in comparative example 2;
fig. 11(b) is an SEM image of the hierarchical porous carbon prepared in comparative example 2.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
Example 1
The embodiment provides a preparation method of graded porous carbon, which comprises the following steps:
(1) grinding and mixing the hard petroleum asphalt and the potassium bicarbonate according to the mass ratio of 1:4 to obtain a uniformly mixed mixture; the initial weight loss temperature of the hard petroleum asphalt is 350 ℃, the weight loss temperature of 80 wt% is between 300 ℃ and 635 ℃, and the weight loss temperature of 95 wt% is 830 ℃;
(2) heating to 800 ℃ at a heating rate of 5 ℃/min under a nitrogen atmosphere, calcining the mixture obtained in the step (1) for 120min, and cooling to room temperature along with a furnace after calcination to obtain a calcined material;
(3) and (3) washing the calcined material obtained in the step (2) until the pH value of a washing liquid is 7, and drying for more than 12h at 60 ℃ to obtain the hierarchical porous carbon named PCNs-800.
As shown in fig. 1(a) and fig. 1(b), the SEM image of the hierarchical porous carbon obtained in this embodiment shows a three-dimensional porous skeleton structure, and shows a rich pore channel structure, which can shorten a diffusion path of lithium ions, reduce diffusion resistance of lithium ions, and provide a rich space for storage of lithium ions.
As shown in fig. 2, it can be seen from fig. 2 that 23 ° and 43 ° in the XRD pattern have two diffraction peaks corresponding to the 002 crystal plane and 100 crystal plane of graphite, and the obtained hierarchical porous carbon has the characteristics of amorphous carbon, and the surface of the hierarchical porous carbon is washed with water to remove the residual templating agent after calcination.
The Raman spectrum of the hierarchical porous carbon obtained in this example is shown in FIG. 3, and as can be seen from FIG. 3, the Raman spectrum is 1350cm -1 And 1590cm -1 The two peaks correspond to the D peak (sp) of the carbon material 2 ) And G peak (sp) 3 ) D Peak to G Peak intensity ratio I D /I G The defect degree is higher than 0.95, so that abundant active sites are provided for the storage of lithium ions, and the defect degree is greatly improvedThe lithium storage capacity of the material is improved, and the capacitance contribution ratio of the material capacity is increased.
Example 2
This example provides a method for preparing graded porous carbon, which is the same as that of example 1 except that the temperature is raised to 600 ℃ at a rate of 5 ℃/min under nitrogen atmosphere, and the obtained graded porous carbon is named PCNs-600.
As shown in fig. 4(a) and 4(b), SEM images of the hierarchical porous carbon obtained in this embodiment show a three-dimensional strip structure with fewer pore channel structures than those of the embodiment.
As shown in fig. 5, it can be seen from fig. 5 that 23 ° and 43 ° in the XRD pattern have two diffraction peaks corresponding to the 002 crystal plane and 100 crystal plane of graphite, and the obtained hierarchical porous carbon has the characteristics of amorphous carbon, and the surface of the hierarchical porous carbon is washed with water to remove the residual templating agent after calcination.
The Raman spectrum of the hierarchical porous carbon obtained in this example is shown in FIG. 6, and it can be seen from FIG. 6 that the Raman spectrum is 1350cm -1 And 1590cm -1 The two peaks respectively correspond to the D peak (sp) of the carbon material 2 ) And G peak (sp) 3 ) D Peak to G Peak intensity ratio I D /I G A value of 0.67, lower than 0.95 in example 1, indicates that the graded porous carbon obtained in this example has a low degree of defects.
Example 3
This example provides a method for preparing a hierarchical porous carbon, which is the same as that of example 1 except that the temperature is raised to 1000 ℃ at a temperature raising rate of 5 ℃/min under a nitrogen atmosphere, and the obtained hierarchical porous carbon is named as PCNs-1000.
SEM images of the obtained hierarchical porous carbon of the present example are shown in fig. 7(a) and 7(b), and the obtained hierarchical porous carbon has a bulk stacked structure, and the pore channel structure is seriously damaged.
As shown in fig. 8, it can be seen from fig. 8 that 23 ° and 43 ° in the XRD pattern have two diffraction peaks corresponding to the 002 crystal plane and 100 crystal plane of graphite, and the obtained hierarchical porous carbon has the characteristics of amorphous carbon, and the surface of the hierarchical porous carbon is washed with water to remove the residual templating agent after calcination. Meanwhile, the intensity of a diffraction peak of a 002 crystal face is enhanced, which shows that the obtained hierarchical porous carbon has higher graphitization degree.
The Raman spectrum of the hierarchical porous carbon obtained in this example is shown in FIG. 9, and as can be seen from FIG. 9, the Raman spectrum is 1350cm -1 And 1590cm -1 The two peaks correspond to the D peak (sp) of the carbon material 2 ) And G peak (sp) 3 ) D Peak to G Peak intensity ratio I D /I G 0.76, lower than example 1 but higher than example 2, indicates a higher degree of graphitization of the hierarchical porous carbon obtained in this example.
Example 4
This example provides a method for preparing hierarchical porous carbon, which is the same as example 1 except that the calcination time in step (2) is 200 min.
Example 5
This example provides a method for preparing hierarchical porous carbon, which is the same as example 1 except that the calcination time in step (2) is 300 min.
Example 6
The embodiment provides a preparation method of graded porous carbon, which comprises the following steps:
(1) grinding and mixing the hard petroleum asphalt and the potassium bicarbonate according to the mass ratio of 1:3 to obtain a mixture; the initial weight loss temperature of the hard petroleum asphalt is 300 ℃, the weight loss is 75 wt% between 300 ℃ and 635 ℃, and the weight loss temperature of 95 wt% is 800 ℃;
(2) heating to 650 ℃ at the heating rate of 4 ℃/min under the helium atmosphere, calcining the mixture obtained in the step (1) for 120min, and cooling to room temperature along with the furnace after the calcination is finished to obtain a calcined material;
(3) and (3) washing the calcined material obtained in the step (2) until the pH value of a washing liquid is 6.7, and drying for more than 12h at 65 ℃ to obtain the hierarchical porous carbon.
Example 7
The embodiment provides a preparation method of graded porous carbon, which comprises the following steps:
(1) grinding and mixing the hard petroleum asphalt and the potassium bicarbonate according to the mass ratio of 1:5 to obtain a mixture; the initial weight loss temperature of the hard petroleum asphalt is 360 ℃, the weight loss temperature of 85 wt% is between 300 ℃ and 635 ℃, and the weight loss temperature of 95 wt% is 850 ℃;
(2) heating to 700 ℃ at a heating rate of 6 ℃/min under a helium atmosphere, calcining the mixture obtained in the step (1) for 120min, and cooling to room temperature along with a furnace after the calcination is finished to obtain a calcined material;
(3) and (3) washing the calcined material obtained in the step (2) with water until the pH value of a washing liquid is 7.2, and drying at 70 ℃ for more than 12h to obtain the hierarchical porous carbon.
Comparative example 1
This comparative example provides a method of preparing a carbon material, the method comprising the steps of:
(1) grinding and mixing the hard petroleum asphalt and the magnesium oxide according to the mass ratio of 1:4 to obtain a mixture; the initial weight loss temperature of the hard petroleum asphalt is 350 ℃, the weight loss is 80 wt% between 300 ℃ and 635 ℃, and the weight loss temperature of 95 wt% is 830 ℃;
(2) heating to 800 ℃ at a heating rate of 5 ℃/min under a nitrogen atmosphere, calcining the mixture obtained in the step (1) for 120min, and cooling to room temperature along with a furnace after calcination to obtain a calcined material;
(3) and (3) removing the residual magnesium oxide after calcination by using deionized water and hydrochloric acid, and drying at 60 ℃ for more than 12h to obtain the carbon material named MOPC-4.
The SEM images of the carbon material obtained in this comparative example are shown in fig. 10(a) and 10(b), and the obtained carbon material has a blocky morphology, and the surface of the block has irregular pores and a deficient pore structure, so that the material exhibits poor lithium storage capacity.
Comparative example 2
This comparative example provides a method of preparing a carbon material, the method comprising the steps of:
(1) grinding and mixing the hard petroleum asphalt and the potassium citrate according to the mass ratio of 1:4 to obtain a mixture; the initial weight loss temperature of the hard petroleum asphalt is 350 ℃, the weight loss is 80 wt% between 300 ℃ and 635 ℃, and the weight loss temperature of 95 wt% is 830 ℃;
(2) heating to 800 ℃ at a heating rate of 5 ℃/min under a nitrogen atmosphere, calcining the mixture obtained in the step (1) for 120min, and cooling to room temperature along with a furnace after calcination to obtain a calcined material;
(3) and (3) removing residual potassium citrate after calcination by using deionized water and hydrochloric acid, and drying at 60 ℃ for more than 12h to obtain the carbon material named HPC-4.
The SEM images of the carbon material obtained in this comparative example are shown in fig. 11(a) and 11(b), and the obtained carbon material has a three-dimensional lamellar structure, and is deficient in internal pores, and only a part of pores exist on the surface of the material, thereby inhibiting the transfer and transport of lithium ions in the bulk phase.
Comparative example 3
This comparative example provides a method of preparing a carbon material, the method comprising the steps of:
(1) grinding and mixing the hard petroleum asphalt and the sodium citrate in a mass ratio of 1:4 to obtain a mixture; the initial weight loss temperature of the hard petroleum asphalt is 350 ℃, the weight loss is 80 wt% between 300 ℃ and 635 ℃, and the weight loss temperature of 95 wt% is 830 ℃;
(2) heating to 800 ℃ at a heating rate of 5 ℃/min under a nitrogen atmosphere, calcining the mixture obtained in the step (1) for 120min, and cooling to room temperature along with a furnace after calcination to obtain a calcined material;
(3) and removing the residual sodium citrate after calcination by using deionized water and hydrochloric acid, and drying at 60 ℃ for more than 12h to obtain the carbon material named as SCC-4.
Comparative example 4
This comparative example provides a method of preparing a carbon material, the method comprising the steps of:
(1) grinding and mixing the hard petroleum asphalt and the magnesium citrate according to the mass ratio of 1:4 to obtain a mixture; the initial weight loss temperature of the hard petroleum asphalt is 350 ℃, the weight loss temperature of 80 wt% is between 300 ℃ and 635 ℃, and the weight loss temperature of 95 wt% is 830 ℃;
(2) heating to 800 ℃ at a heating rate of 5 ℃/min under a nitrogen atmosphere, calcining the mixture obtained in the step (1) for 120min, and cooling to room temperature along with a furnace after calcination to obtain a calcined material;
(3) and (3) removing the residual magnesium citrate after calcination by using deionized water and hydrochloric acid, and drying at 60 ℃ for more than 12 hours to obtain the carbon material named MCC-4.
Comparative example 5
This comparative example provides a method of preparing a carbon material, the method comprising the steps of:
(1) grinding and mixing the hard petroleum asphalt and the magnesium acetate according to the mass ratio of 1:4 to obtain a mixture; the initial weight loss temperature of the hard petroleum asphalt is 350 ℃, the weight loss temperature of 80 wt% is between 300 ℃ and 635 ℃, and the weight loss temperature of 95 wt% is 830 ℃;
(2) heating to 800 ℃ at a heating rate of 5 ℃/min in a nitrogen atmosphere, calcining the mixture obtained in the step (1) for 120min, and cooling to room temperature along with a furnace after the calcination is finished to obtain a calcined material;
(3) and (3) removing the residual magnesium acetate after calcination by using deionized water and hydrochloric acid, and drying at 60 ℃ for more than 12 hours to obtain the carbon material named as MAC-4.
Comparative example 6
The present comparative example provides a method for producing a carbon material, the method comprising the steps of:
(1) grinding and mixing the hard petroleum asphalt and the potassium acetate according to the mass ratio of 1:4 to obtain a mixture; the initial weight loss temperature of the hard petroleum asphalt is 350 ℃, the weight loss is 80 wt% between 300 ℃ and 635 ℃, and the weight loss temperature of 95 wt% is 830 ℃;
(2) heating to 800 ℃ at a heating rate of 5 ℃/min under a nitrogen atmosphere, calcining the mixture obtained in the step (1) for 120min, and cooling to room temperature along with a furnace after calcination to obtain a calcined material;
(3) and removing residual potassium acetate after calcination by using deionized water and hydrochloric acid, and drying at 60 ℃ for more than 12h to obtain the carbon material, which is named as PAC-4.
Application example 1
The application example provides a button battery, wherein a negative pole piece of the button battery comprises a copper foil and an electrode active material coated on the copper foil, and the electrode active material comprises the hierarchical porous carbon, conductive carbon black and polyvinylidene fluoride obtained in the embodiment 1; the button cell takes a lithium sheet as a reference electrode to prepare a CR2025 type button cell.
The mass ratio of the hierarchical porous carbon to the conductive carbon black to the polyvinylidene fluoride is 8:1: 1.
The coating amount of the electrode active material on the aluminum foil is as follows: the mass density of the graded porous carbon is 1mg/cm 2 。
Application example 2
This application example provides a button cell, which is the same as application example 1 except that the hierarchical porous carbon is the hierarchical porous carbon provided in example 2.
Application example 3
This application example provides a button cell, which is the same as application example 1 except that the hierarchical porous carbon is the hierarchical porous carbon provided in example 3.
Application example 4
This application example provides a button cell, which is the same as application example 1 except that the hierarchical porous carbon is the hierarchical porous carbon provided in example 4.
Application example 5
This application example provides a button cell, which is the same as application example 1 except that the hierarchical porous carbon is the hierarchical porous carbon provided in example 5.
Application example 6
This application example provides a button cell, which is the same as application example 1 except that the hierarchical porous carbon is the hierarchical porous carbon provided in example 6.
Application example 7
This application example provides a button cell, which was the same as application example 1 except that the hierarchical porous carbon was the hierarchical porous carbon provided in example 7.
Comparative application example 1
This comparative application example provides a button cell, which was the same as application example 1 except that the graded porous carbon was replaced with the same mass of the carbon material provided in comparative example 1.
Comparative application example 2
This comparative application example provides a button cell, which was the same as application example 1 except that the graded porous carbon was replaced with the carbon material of equal mass as provided in comparative example 2.
Comparative application example 3
This comparative application example provides a button cell, which was the same as application example 1 except that the graded porous carbon was replaced with the carbon material of equal mass as provided in comparative example 3.
Comparative application example 4
This comparative application example provides a button cell, which was the same as application example 1 except that the graded porous carbon was replaced with the carbon material of equal mass as provided in comparative example 4.
Comparative application example 5
This comparative application example provides a button cell identical to application example 1 except that the graded porous carbon was replaced with the equal mass of the carbon material provided in comparative example 5.
Comparative application example 6
This comparative application example provides a button cell, which was the same as application example 1 except that the graded porous carbon was replaced with the carbon material of equal mass as provided in comparative example 6.
Comparative application example 7
This comparative application example provides a button cell, which was the same as in application example 1 except that the graded porous carbon was replaced with commercial graphite of equal mass.
The specific capacities of the button cells provided in application examples 1 to 7 and comparative application examples 1 to 7 at a current density of 1A/g were measured, and the results are shown in Table 1.
TABLE 1
Figure BDA0002793893630000161
Figure BDA0002793893630000171
As can be seen from table 1, the hierarchical porous carbon prepared by the preparation method of the present invention has excellent negative electrode lithium storage performance, and compared with carbon materials prepared from commercial graphite and other materials, the negative electrode lithium storage performance of the hierarchical porous carbon prepared in examples 1 to 7 is significantly improved.
Application example I
The application example provides a button battery, wherein a positive electrode plate of the button battery comprises an aluminum foil and an electrode active material coated on the aluminum foil, and the electrode active material comprises the hierarchical porous carbon, conductive carbon black and polyvinylidene fluoride obtained in the embodiment 1; the button cell takes a lithium sheet as a reference electrode to prepare a CR2025 type button cell.
The mass ratio of the hierarchical porous carbon to the conductive carbon black to the polyvinylidene fluoride is 8:1: 1.
The coating amount of the electrode active material on the aluminum foil is as follows: the mass density of the graded porous carbon is 1mg/cm 2 。
Application example II
This application example provides a button cell that is the same as application example I except that the hierarchical porous carbon is the hierarchical porous carbon provided in example 2.
Application example III
This application example provides a button cell that is the same as application example I except that the hierarchical porous carbon is the hierarchical porous carbon provided in example 3.
Application example IV
This application example provides a button cell that is the same as application example I except that the hierarchical porous carbon is the hierarchical porous carbon provided in example 4.
Application example V
This application example provides a button cell, which is the same as application example I except that the hierarchical porous carbon is the hierarchical porous carbon provided in example 5.
Application example VI
This application example provides a button cell that is the same as application example I except that the hierarchical porous carbon is the hierarchical porous carbon provided in example 6.
Application example VII
This application example provides a button cell that is the same as application example I except that the graded porous carbon is the graded porous carbon provided in example 7.
Comparative application example I
This comparative application example provides a button cell identical to application example I except that the graded porous carbon was replaced with the same mass of the carbon material provided in comparative example 1.
Comparative application example II
This comparative application example provides a button cell identical to application example I except that the graded porous carbon was replaced with the same mass of the carbon material provided in comparative example 2.
Comparative application example III
This comparative application example provides a button cell identical to application example I except that the graded porous carbon was replaced with the equal mass of the carbon material provided in comparative example 3.
Comparative application example IV
This comparative application example provides a button cell identical to application example I except that the graded porous carbon was replaced with the equal mass of the carbon material provided in comparative example 4.
Comparative application example V
This comparative application example provides a button cell identical to application example I except that the graded porous carbon was replaced with the equal mass of the carbon material provided in comparative example 5.
Comparative application example VI
This comparative application example provides a button cell identical to application example I except that the graded porous carbon was replaced with the same mass of the carbon material provided in comparative example 6.
Comparative application example VII
This comparative application example provides a button cell, which is the same as application example I except that the graded porous carbon was replaced with commercial graphite of equal mass.
Test application examples I-VII and comparative application examples I-VII the button cells provided were tested for electrochemical performance and the results are shown in table 2.
TABLE 2
Figure BDA0002793893630000191
Figure BDA0002793893630000201
As can be seen from table 2, the hierarchical porous carbon prepared by the preparation method of the present invention has excellent positive lithium storage performance, and compared with carbon materials prepared from commercial graphite and other materials, the positive lithium storage performance of the hierarchical porous carbon prepared in examples 1 to 7 is significantly improved.
Application example A
The application example provides a lithium ion capacitor, wherein a positive pole piece of the lithium ion capacitor is the positive pole piece provided by the application example I, a negative pole piece of the lithium ion capacitor is the negative pole piece provided by the application example 1, and the electrolyte is a conventional lithium ion battery electrolyte sold in the market.
Wherein the mass ratio of the positive pole piece to the negative pole piece is 1: 1.
Application example B
The application example provides a lithium ion capacitor, wherein a positive pole piece of the lithium ion capacitor is the positive pole piece provided by the application example II, a negative pole piece of the lithium ion capacitor is the negative pole piece provided by the application example 2, and the rest is the same as the application example A.
Application example C
The application example provides a lithium ion capacitor, wherein a positive pole piece of the lithium ion capacitor is the positive pole piece provided by the application example III, a negative pole piece of the lithium ion capacitor is the negative pole piece provided by the application example 3, and the rest is the same as the application example A.
Application example D
The application example provides a lithium ion capacitor, wherein a positive pole piece of the lithium ion capacitor is the positive pole piece provided by the application example IV, a negative pole piece of the lithium ion capacitor is the negative pole piece provided by the application example 4, and the rest is the same as the application example A.
Application example E
The application example provides a lithium ion capacitor, wherein a positive pole piece of the lithium ion capacitor is the positive pole piece provided by the application example V, a negative pole piece of the lithium ion capacitor is the negative pole piece provided by the application example 5, and the rest is the same as the application example A.
Application example F
The application example provides a lithium ion capacitor, wherein a positive pole piece of the lithium ion capacitor is the positive pole piece provided by the application example VI, a negative pole piece of the lithium ion capacitor is the negative pole piece provided by the application example 6, and the rest is the same as the application example A.
Application example G
The application example provides a lithium ion capacitor, wherein a positive electrode piece of the lithium ion capacitor is the positive electrode piece provided by the application example VII, a negative electrode piece of the lithium ion capacitor is the negative electrode piece provided by the application example 7, and the rest are the same as the application example A.
Application example H
The application example provides a lithium ion capacitor, and the mass ratio of the positive pole piece to the negative pole piece is 1:2, and the rest is the same as the application example A.
Application example J
The application example provides a lithium ion capacitor, and the mass ratio of the positive pole piece to the negative pole piece is 2:1, and the rest is the same as the application example A.
And testing the electrochemical performance of the lithium ion capacitor. The results obtained are shown in Table 3.
TABLE 3
Figure BDA0002793893630000221
As can be seen from Table 3, the lithium ion capacitors provided in application examples A-G have higher energy density at a power density of 260W/kg, and the cycle retention rate after 9000 cycles can reach 70%. By comparing the application examples H and J, it can be seen that the lithium ion capacitor constructed when the mass ratio of the positive electrode plate to the negative electrode plate is the same has the optimal electrochemical performance.
In conclusion, the invention uses the petroleum asphalt as the byproduct of the petroleum refining process, compared with the industrial preparation of the activated carbon raw material, the price is low, the source is wide, and the high carbon content leads the yield of the prepared porous carbon product to be higher; the bicarbonate used in the invention conforms to the development concept of environmental protection, the potassium carbonate generated in the calcining process can be directly removed by water, and the method is green and pollution-free, effectively reduces the production cost, and has very considerable large-scale application prospect; the bicarbonate used in the invention has extremely low equipment corrosivity, and an acid reagent is not required to be introduced to remove the template and the activating agent, so that the industrial production flow and energy consumption are greatly reduced; the hierarchical porous carbon can be used as a positive active material and a negative active material of a metal ion capacitor at the same time, and the positive active material and the negative active material comprising the hierarchical porous carbon have good cycling stability, ideal coulombic efficiency and high energy density.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (20)

1. A preparation method of hierarchical porous carbon is characterized by comprising the following steps:
(1) uniformly mixing petroleum asphalt and bicarbonate according to the mass ratio of 1 (3-5) to obtain a mixture; the petroleum asphalt is hard petroleum asphalt, the initial weight loss temperature of the hard petroleum asphalt is more than or equal to 300 ℃, the weight loss between 300 ℃ and 635 ℃ is more than or equal to 75 wt%, and the weight loss temperature of 95 wt% is more than or equal to 800 ℃;
(2) calcining the mixture obtained in the step (1) in a protective atmosphere, and cooling to room temperature after calcination to obtain a calcined material; the calcination temperature is 650-800 ℃, the heating rate is 3-6 ℃/min, and the time is 120-300 min;
(3) and (3) washing the calcined material obtained in the step (2) with water, and drying to obtain the hierarchical porous carbon.
2. The method according to claim 1, wherein the bicarbonate in step (1) is potassium bicarbonate.
3. The method according to claim 1, wherein the mixing in step (1) is a milling mixing.
4. The method of claim 3, wherein the milling and mixing comprises hand milling or dry ball milling.
5. The method according to claim 1, wherein the protective atmosphere in step (2) is a nitrogen atmosphere and/or an inert atmosphere.
6. The method according to claim 1, wherein the cooling in step (2) is furnace cooling.
7. The production method according to claim 1, wherein the end point of the water washing in the step (3) is a pH value of the water washing solution of 6.5 to 7.5.
8. The method according to claim 1, wherein the drying temperature in the step (3) is 60 to 70 ℃.
9. The method of claim 1, wherein the drying time in step (3) is 12h or more.
10. The method of claim 1, comprising the steps of:
(1) grinding and mixing the hard petroleum asphalt and the bicarbonate according to the mass ratio of 1 (3-5) to obtain a uniformly mixed mixture; the initial weight loss temperature of the hard petroleum asphalt is more than or equal to 300 ℃, the weight loss between 300 ℃ and 635 ℃ is more than or equal to 75 wt%, and the weight loss temperature of 95 wt% is more than or equal to 800 ℃;
(2) heating to 650-800 ℃ at the heating rate of 3-6 ℃/min under the protective atmosphere, calcining the mixture obtained in the step (1) for 300min, and cooling to room temperature along with the furnace after the calcination is finished to obtain a calcined material;
(3) and (3) washing the calcined material obtained in the step (2) until the pH value of a washing liquid is 6.5-7.5, and drying at 60-70 ℃ for more than 12h to obtain the hierarchical porous carbon.
11. A hierarchical porous carbon prepared by the preparation method as set forth in any one of claims 1 to 10.
12. Use of the hierarchical porous carbon according to claim 11 for metal ion capacitors, secondary batteries or electrical devices.
13. Use according to claim 12, wherein the metal ion capacitor is a lithium ion capacitor;
the positive pole piece of the lithium ion capacitor comprises an aluminum foil and an electrode active material coated on the aluminum foil; the negative pole piece of the lithium ion capacitor comprises a copper foil and an electrode active material coated on the copper foil;
the electrode active material comprises the hierarchical porous carbon of claim 11.
14. The use of claim 13, wherein the mass ratio of the positive electrode piece to the negative electrode piece is (1-2) to (1-2).
15. The use of claim 14, wherein the mass ratio of the positive pole piece to the negative pole piece is 1: 1.
16. Use according to claim 13, characterized in that the electrode active material comprises graded porous carbon, conductive carbon black and polyvinylidene fluoride.
17. The use according to claim 13, characterized in that the mass density of the graded porous carbon on the positive pole piece is 0.4-3mg/cm 2 。
18. The use according to claim 17, characterized in that the mass density of the graded porous carbon on the positive electrode sheet is 0.5-1mg/cm 2 。
19. Root of herbaceous plantThe use according to claim 13, characterized in that the mass density of the graded porous carbon on the negative electrode sheet is 0.4-3mg/cm 2 。
20. The use according to claim 19, wherein the mass density of the graded porous carbon on the negative electrode sheet is 0.5-1mg/cm 2 。
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