CN114620722B - Porous carbon negative electrode material, preparation method thereof, electrode, battery and capacitor prepared from porous carbon negative electrode material - Google Patents

Porous carbon negative electrode material, preparation method thereof, electrode, battery and capacitor prepared from porous carbon negative electrode material Download PDF

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CN114620722B
CN114620722B CN202210262543.5A CN202210262543A CN114620722B CN 114620722 B CN114620722 B CN 114620722B CN 202210262543 A CN202210262543 A CN 202210262543A CN 114620722 B CN114620722 B CN 114620722B
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porous carbon
carbon
molten salt
electrode material
anode material
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CN114620722A (en
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刘冰
李文斐
陈保磊
郅立鹏
迟淑丽
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Qingdao Naboke Environmental Protection Technology Co ltd
Qingdao Huashijie Environment Protection Technology Co ltd
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Qingdao Naboke Environmental Protection Technology Co ltd
Qingdao Huashijie Environment Protection Technology Co ltd
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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
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
    • H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes

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Abstract

The invention provides a porous carbon anode material and a preparation method thereof, and an electrode, a battery and a capacitor prepared from the porous carbon anode material, and belongs to the technical field of battery anode materials. Wherein, the raw materials for preparing the porous carbon cathode material are porous carbon and molten salt; the preparation method comprises the following steps: mixing porous carbon with molten salt, performing high-temperature treatment under inert atmosphere, cooling, washing, separating and drying to obtain the porous carbon anode material; the porous carbon anode material prepared by the method of the invention has high ion capacity and high first charge and discharge efficiency, and also has good ion diffusion channel, thus having high multiplying power performance.

Description

Porous carbon negative electrode material, preparation method thereof, electrode, battery and capacitor prepared from porous carbon negative electrode material
Technical Field
The invention belongs to the technical field of battery cathode materials, and particularly relates to a porous carbon cathode material and a preparation method thereof, and an electrode prepared from the porous carbon cathode material, a battery prepared from the electrode and a capacitor prepared from the electrode.
Background
The current negative electrode materials for lithium ion batteries mainly comprise modified natural graphite and artificial graphite, the capacity of the graphite negative electrode materials in the prior art is close to the theoretical value allowed by the structure, so that the continuous development of energy density faces a bottleneck, meanwhile, the capacity of graphite in a sodium ion battery is too low to be practical, and the amorphous carbon material is considered to be the negative electrode material which is favorable for improving the energy and power density due to the fact that the structure is not limited by the theory, and is expected to be applied to the fields of lithium ion batteries, supercapacitors, sodium ion batteries and the like.
The porous carbon material is considered to be beneficial to improving the capacity of active ions and shows higher first capacity due to rich pore structures, however, the existing porous carbon material generally has the defect of low first charge-discharge efficiency, and the specific reason is not considered to be related to large surface area and many defects at present, so that the first charge-discharge efficiency is low, the utilization rate of the anode material is reduced, the utilization rate of the anode material and the electrolyte is reduced, and the improvement of energy density and the reduction of cost are not facilitated.
In the prior art, the porous carbon material is prepared by adopting oxide, hydroxide or salt, but the introduction purposes are different, the operation steps are different, and therefore, the effect of the invention cannot be obtained. For example, oxides and hydroxides typically have relatively high melting points and cannot enter the porous carbon channels in a liquid state, and the structure forms a support; the oxide and hydroxide with lower melting points can form liquid state, but have high reactivity, and can not maintain the pore canal structure of the porous carbon; and the salt is used as a pore-forming agent, so that the salt mainly plays a role in the activation pore-forming process, and the temperature in the activation process is insufficient for forming a liquid support pore structure, and the effect of improving the primary charge and discharge efficiency is also insufficient.
In order to improve the first charge and discharge efficiency of the porous carbon material, the material is generally treated by adopting a high-temperature inert atmosphere, the obtained material generally has larger platform capacity, the specific reason is not known, the effect is generally improved due to proper graphite interlayer spacing and smaller pore diameter, but the platform capacity is easily influenced by polarization effect during high-current discharge, so the multiplying power performance of the material is generally lower.
Based on the above technical problems, there is a need for a porous carbon material with higher rate capability while contributing to the improvement of the first charge and discharge efficiency.
Disclosure of Invention
The invention aims to provide a porous carbon anode material, a preparation method thereof, and an electrode, a battery and a capacitor prepared from the porous carbon anode material, so as to solve the technical problem that the existing porous carbon material serving as the anode material generally presents lower first charge and discharge efficiency and rate capability.
In order to achieve the above purpose, the invention provides a porous carbon anode material, wherein the raw materials for preparing the porous carbon anode material comprise porous carbon and molten salt.
The invention provides a preparation method of the porous carbon anode material, which comprises the following steps: and mixing the porous carbon with molten salt, performing high-temperature treatment under inert atmosphere, cooling, washing, separating and drying to obtain the porous carbon anode material.
The inert atmosphere may be nitrogen or argon.
Further, the molten salt comprises one or more of compounds with a melting point of less than or equal to 1000 ℃ and a boiling point of more than or equal to 1300 ℃; or the molten salt comprises one or more compounds with melting point less than or equal to 1000 ℃ and boiling point more than or equal to 1300 ℃ as decomposed or reacted products.
Preferably, the molten salt comprises one or more of sodium chloride, potassium chloride, magnesium chloride or calcium chloride.
The porous carbon comprises one or more of a carbon material obtained by activating a carbon-containing precursor through a physical or chemical method and an intermediate product activated by the carbon-containing precursor.
Preferably, the porous carbon comprises one or more of coal activated carbon, coconut activated carbon, activated carbon fiber, and carbon molecular sieve.
Mixing the porous carbon with molten salt, wherein the mixing is liquid phase mixing or solid phase mixing.
Preferably, the liquid phase mixing is an equal volume impregnation or an excess impregnation of the porous carbon after the molten salt is formulated into a solution.
Preferably, the solid phase mixing is a combination of one or more of rolling, ball milling or sanding the porous carbon with the molten salt.
More preferably, the ratio of the porous carbon to the molten salt mass in the solid phase mixing is 1:10 to 10:1.
For the high temperature treatment, optionally, the high temperature treatment is one or a combination of two of batch or continuous;
optionally, the high temperature treatment is one or a combination of internal heating or external heating;
optionally, the high temperature treatment apparatus comprises one or more of a rotary heating furnace, a tube furnace, a tunnel kiln, or an induction furnace;
further, the temperature of the high-temperature treatment is 800-1800 ℃, but the temperature is not too high, so that the high-temperature treatment is prevented from escaping from porous carbon pore channels and losing the supporting effect on the structure; the high temperature treatment time is 0.1-10h. The reason is that the high temperature is helpful to improve the first charge and discharge efficiency, and meanwhile, the maintenance of the pore channel structure of the porous carbon material is helpful to ion diffusion, so that the polarization effect has small influence, and the multiplying power performance can be improved.
Preferably, the high temperature treatment is to raise the temperature to 800-1000 ℃ firstly, react for 0.1-2h, then raise the temperature to 1300-1800 ℃ and stay for 0.5-8h. The first section of heating can enable molten salt to be melted into porous carbon pore channels; the porous carbon can obtain high rate performance by the second-stage heating, and the high-temperature treatment process can obtain better effect by the two-stage heating mode.
In the preparation method, optionally, the cooling is one or the combination of two of natural cooling or refrigerant forced cooling;
optionally, the washing is one or a combination of several of water washing, solvent washing or supercritical washing;
optionally, the separation is a combination of one or both of filtration or centrifugation;
optionally, the drying is one or a combination of vacuum drying, heat drying or freeze drying.
An electrode material comprises the porous carbon anode material.
A battery comprising said electrode material.
A capacitor comprising said electrode material.
According to the invention, the porous carbon and the molten salt are mixed and then subjected to a series of treatments to change the structure of the porous carbon to obtain the porous carbon anode material, and the molten salt is converted into a liquid state at a certain temperature, enters porous carbon pore channels and supports the pore structure of the material in the subsequent treatment process with higher temperature, so that the ion capacity and the first charge and discharge efficiency are improved, and the porous carbon anode material also has a good ion diffusion channel and high rate performance; the anode material of the battery obtained by adopting the porous carbon anode material has excellent first charge and discharge efficiency and rate capability, can also improve the utilization rate of anode and cathode materials and electrolyte, and reduces the cost.
Detailed Description
The term as used herein:
"prepared from … …" is synonymous with "comprising". The terms "comprising," "including," "having," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, 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, step, method, article, or apparatus.
The conjunction "consisting of … …" excludes any unspecified element, step or component. If used in a claim, such phrase will cause the claim to be closed, such that it does not include materials other than those described, except for conventional impurities associated therewith. When the phrase "consisting of … …" appears in a clause of the claim body, rather than immediately following the subject, it is limited to only the elements described in that clause; other elements are not excluded from the stated claims as a whole.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list 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 ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range.
In these examples, the parts and percentages are by mass unless otherwise indicated.
"parts by mass" means a basic unit of measurement showing the mass ratio of a plurality of components, and 1 part may be any unit mass, for example, 1g may be expressed, 2.689g may be expressed, and the like. If we say that the mass part of the a component is a part and the mass part of the B component is B part, the ratio a of the mass of the a component to the mass of the B component is represented as: 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 not misunderstood that the sum of the parts by mass of all the components is not limited to 100 parts, unlike the parts by mass.
"and/or" is used to indicate that one or both of the illustrated cases may occur, e.g., a and/or B include (a and B) and (a or B).
The embodiment of the invention provides a porous carbon anode material, a preparation method of the porous carbon anode material, an electrode, a battery and a capacitor prepared from the porous carbon anode material, wherein the preparation method of the porous carbon anode material comprises the following steps of: and mixing the porous carbon with molten salt, performing high-temperature treatment under inert atmosphere, cooling, washing, separating and drying to obtain the porous carbon anode material. Wherein the molten salt comprises one or more of compounds with a melting point less than or equal to 1000 ℃ and a boiling point more than or equal to 1300 ℃; or the molten salt comprises one or more compounds with melting point less than or equal to 1000 ℃ and boiling point more than or equal to 1300 ℃ as decomposed or reacted products. The porous carbon comprises one or more of a carbon material obtained by activating a carbon-containing precursor through a physical or chemical method and an intermediate product activated by the carbon-containing precursor.
As a preferred embodiment, the molten salt comprises one or more of sodium chloride, potassium chloride, magnesium chloride or calcium chloride; the porous carbon comprises one or more of coal activated carbon, coconut activated carbon, activated carbon fiber and carbon molecular sieve.
In the embodiment of the invention, the porous carbon is mixed with the molten salt, and the mixing is liquid phase mixing or solid phase mixing. As a preferred embodiment, the liquid phase mixing is to impregnate or overdose porous carbon with equal volume after preparing molten salt into solution; the solid phase mixing is the combination of one or more than two of rolling, ball milling or sanding of the porous carbon and the molten salt; the mass ratio of the porous carbon to the molten salt in the solid phase mixing is 1:10-10:1. Sodium chloride and potassium chloride are not limited by the mixing mode, and magnesium chloride and calcium chloride are not suitable for liquid phase mixing because they are easy to hydrolyze to form magnesium hydroxide and calcium hydroxide.
The high temperature treatment in the embodiment of the invention is one or the combination of two of batch type and continuous type; the high temperature treatment is one or the combination of two of internal heating or external heating; the high-temperature treatment equipment comprises one of a rotary heating furnace, a tubular furnace, a tunnel kiln or an induction furnace; the high-temperature treatment time is 0.1-10h; the temperature of the high-temperature treatment is 800-1800 ℃.
As a more preferred embodiment, the high temperature treatment is to raise the temperature to 800-1000 ℃ firstly, react for 0.1-2h, then raise the temperature to 1300-1800 ℃ and stay for 0.5-8h.
Molten salt is converted into liquid state at high temperature and enters porous carbon pore canal, and the pore structure of the material is supported in the subsequent higher temperature treatment process, so that the porous carbon has high ion capacity and high first charge and discharge efficiency, and also has a good ion diffusion channel, so that the porous carbon has high multiplying power performance.
In the embodiment of the invention, the cooling is one or the combination of two of natural cooling or refrigerant forced cooling; the washing is one or a combination of more of water washing, solvent washing or supercritical washing; the separation is a combination of one or both of filtration or centrifugation; the drying is one or a combination of vacuum drying, heating drying or freeze drying.
In the embodiment of the invention, the carbon content of the porous carbon anode material is more than 98 percent, N 2 Specific surface area greater than 300m 2 The proportion of micropores is larger than 80%, and the pore volume of micropores is larger than 0.6cm 3 /g。
The embodiment of the invention also provides an electrode material, which comprises the porous carbon anode material. The electrode containing the porous carbon negative electrode material comprises other auxiliary components such as a binder, a conductive agent and the like which are well known to the person skilled in the art.
The embodiment of the invention also provides a battery, which comprises the electrode material. The battery comprising the above electrode, other parts include positive electrode, separator, electrolyte, additives, and the like, which are well known to those skilled in the art.
The embodiment of the invention also provides a capacitor, which comprises the electrode material. The capacitor comprising the above electrode, other parts include electrolytic solutions, electrolytes, separators, and the like, which are well known to those skilled in the art.
Embodiments of the present invention will be described in detail below with reference to specific examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
The embodiment provides a preparation method of a porous carbon anode material, which comprises the following steps: mixing sodium chloride (melting point 801 ℃ and boiling point 1413 ℃) with coal-made active carbon liquid phase (preparing sodium chloride into solution and then excessively soaking the coal-made active carbon), carrying out high-temperature treatment by adopting a tube furnace under inert atmosphere, wherein the temperature is 1000 ℃ for 10 hours, naturally cooling, washing with water, filtering, and vacuum drying at 80 ℃ to obtain the porous carbon anode material.
Through testing, the carbon content of the obtained porous carbon anode material is 98.3 percent, N 2 Specific surface area of 320m 2 Per gram, the micropore ratio is 85%, and the micropore volume is 0.63cm 3 /g。
The porous carbon anode material is used as an anode of a CR2032 battery assembled by taking a sodium metal sheet as a counter electrode and taking 1M NaPF6-EC/DMC (1:1v/v) as electrolyte, and has a first reversible capacity of 455mah/g, a first charge-discharge efficiency of 89% and a first charge-discharge efficiency of 85% and a first charge-discharge efficiency of 0.5C/0.2C.
Example 2
The embodiment provides a preparation method of a porous carbon anode material, which comprises the following steps: mixing potassium chloride (melting point 770 ℃ and boiling point 1420 ℃) and coconut shell active carbon in a ratio of 3:1 by rolling and solid phase, carrying out high-temperature treatment by adopting a rotary heating furnace under inert atmosphere at 1350 ℃ for 5 hours, then cooling by a refrigerant forcibly, washing by water, centrifuging, separating, and drying in vacuum at 80 ℃ to obtain the porous carbon anode material.
Through analysis and test, the carbon content of the obtained porous carbon anode material is 98.8 percent, N 2 Specific surface area of 330m 2 Per gram, the micropore ratio is 87%, and the micropore volume is 0.67cm 3 /g。
The porous carbon anode material is used as an anode of a CR2032 battery assembled by taking a sodium metal sheet as a counter electrode and taking 1M NaPF6-EC/DMC (1:1v/v) as electrolyte, and has 460mah/g of first reversible capacity, 90% of first charge-discharge efficiency and 85.3% of 0.5C/0.2C.
Example 3
The embodiment provides a preparation method of a porous carbon anode material, which comprises the following steps: mixing magnesium chloride (melting point 714 ℃ and boiling point 1412 ℃) and carbon molecular sieve in a ratio of 4:1 through ball milling and solid phase, adopting a rotary heating furnace to carry out high-temperature treatment under inert atmosphere at 1400 ℃ for 1h, naturally cooling, washing with water, filtering, and freeze-drying at 80 ℃ to obtain the porous carbon anode material.
Through analysis and test, the carbon content of the obtained porous carbon anode material is 99 percent, N 2 Specific surface area of 350m 2 The proportion of micropores is 89%, and the pore volume of micropores is 0.72cm 3 /g。
The porous carbon anode material is used as an anode of a CR2032 battery assembled by taking a sodium metal sheet as a counter electrode and taking 1M NaPF6-EC/DMC (1:1v/v) as electrolyte, and has the first reversible capacity of 430mah/g, the first charge-discharge efficiency of 90 percent and the first charge-discharge efficiency of 85.7 percent.
Example 4
The embodiment provides a preparation method of a porous carbon anode material, which comprises the following steps: mixing calcium chloride (melting point 782 ℃ and boiling point 1600 ℃ or above) and active carbon fiber in a ratio of 6:1 through ball milling and solid phase, performing high-temperature treatment by adopting a rotary heating furnace under inert atmosphere at 1580 ℃ for 8 hours, naturally cooling, washing with water, filtering, and vacuum drying at 80 ℃ to obtain the porous carbon anode material.
Through analysis and test, the carbon content of the obtained porous carbon anode material is 98 percent, N 2 A specific surface area of 337m 2 Per gram, the micropore ratio is 87%, and the micropore volume is 0.69cm 3 /g。
The porous carbon anode material is used as an anode of a CR2032 battery assembled by taking a sodium metal sheet as a counter electrode and taking 1M NaPF6-EC/DMC (1:1v/v) as electrolyte, and has the first reversible capacity of 480mah/g, the first charge-discharge efficiency of 93 percent and the first charge-discharge efficiency of 86 percent.
Example 5
The embodiment provides a preparation method of a porous carbon anode material, which comprises the following steps: mixing calcium chloride (melting point 782 ℃ and boiling point 1600 ℃ or above) and active carbon fiber in a ratio of 10:1 by ball milling and solid phase, heating to 900 ℃ by adopting a rotary heating furnace under inert atmosphere, reacting for 1h, and then heating to 1800 ℃ and staying for 3h. And naturally cooling, washing with water, filtering, and vacuum drying at 80 ℃ to obtain the porous carbon anode material.
Through analysis and test, the carbon content of the obtained porous carbon anode material is 99 percent, N 2 A specific surface area of 423m 2 Per gram, the micropore ratio is 90%, and the micropore volume is 0.68cm 3 /g。
The porous carbon anode material is used as an anode of a CR2032 battery assembled by taking a sodium metal sheet as a counter electrode and taking 1M NaPF6-EC/DMC (1:1v/v) as electrolyte, and has 485mah/g first reversible capacity, the first charge-discharge efficiency is 95%, and the first charge-discharge efficiency is 88% at 0.5C/0.2C.
Based on the above part of the exemplary embodiments extracted from the experimental data, it can be seen that, for the porous carbon, the properties of the obtained porous carbon anode material are as follows in order from low to high: coal activated carbon, coconut activated carbon, carbon molecular sieve and activated carbon fiber. The higher the temperature within the operating range, the better the performance in terms of temperature. For the proportion of the molten salt to the activated carbon, the proportion of the molten salt needed by the activated carbon of different types is different, and the ordering of the porous carbon raw materials can be basically referred, when the using amount of the molten salt is sufficient (at least 2:1), the structure of the activated carbon is relatively complete, the performance is better, and when the molten salt is excessive, the structure protection is not additionally improved; when the molten salt is insufficient, the active carbon structure can partially collapse, and the performance is reduced.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features but not others included in other embodiments, 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 below, 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 (8)

1. A preparation method of a porous carbon negative electrode material is characterized in that porous carbon and molten salt are mixed, high-temperature treatment is carried out under inert atmosphere, washing, separation and drying are carried out after cooling, and the porous carbon negative electrode material is obtained, wherein the carbon content of the porous carbon negative electrode material is more than 98 percent, and N is greater than 2 Specific surface area greater than 300m 2 The proportion of micropores is larger than 80%, and the pore volume of micropores is larger than 0.6cm 3 /g；
The porous carbon comprises one or more of coal activated carbon, coconut activated carbon, activated carbon fiber and carbon molecular sieve, and the molten salt comprises one or more of sodium chloride, potassium chloride, magnesium chloride or calcium chloride;
the mass ratio of the porous carbon to the molten salt in the mixing is 1:10-10:1;
the high temperature treatment is to raise the temperature to 800-1000 ℃ for reaction for 0.1-2h, then raise the temperature to 1300-1800 ℃ and stay for 0.5-8h.
2. The method of claim 1, wherein the porous carbon comprises one or more of a carbon material obtained by physical or chemical activation of a carbon-containing precursor, and an intermediate product of activation of a carbon-containing precursor.
3. The method of producing according to claim 1, wherein the porous carbon is mixed with molten salt, the mixing being liquid phase mixing or solid phase mixing;
the liquid phase mixing is to prepare molten salt into solution and then to impregnate porous carbon in equal volume or excessive amount;
the solid phase mixing is a combination of one or more of rolling, ball milling or sanding the porous carbon and the molten salt.
4. The method of claim 1, wherein the high temperature treatment satisfies one or more of the following conditions:
a. the high temperature treatment is one or the combination of two of internal heating or external heating;
b. the high temperature treatment equipment comprises one or more of a rotary heating furnace, a tube furnace, a tunnel kiln or an induction furnace.
5. The method of manufacturing of claim 1, further satisfying one or more of the following conditions:
c. the cooling is one or the combination of two of natural cooling or refrigerant forced cooling;
d. the washing is one or a combination of more of water washing, solvent washing or supercritical washing;
e. the separation is a combination of one or both of filtration or centrifugation;
f. the drying is one or a combination of vacuum drying, heating drying or freeze drying.
6. An electrode material characterized by comprising the porous carbon anode material produced by the method for producing a porous carbon anode material according to any one of claims 1 to 5.
7. A battery comprising the electrode material of claim 6.
8. A capacitor comprising the electrode material of claim 6.
CN202210262543.5A 2022-03-17 2022-03-17 Porous carbon negative electrode material, preparation method thereof, electrode, battery and capacitor prepared from porous carbon negative electrode material Active CN114620722B (en)

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