CN114620722A - 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 PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 113
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000003990 capacitor Substances 0.000 title claims abstract description 11
- 150000003839 salts Chemical class 0.000 claims abstract description 39
- 238000002156 mixing Methods 0.000 claims abstract description 33
- 238000011282 treatment Methods 0.000 claims abstract description 31
- 238000005406 washing Methods 0.000 claims abstract description 21
- 238000001816 cooling Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 19
- 238000002844 melting Methods 0.000 claims description 13
- 230000008018 melting Effects 0.000 claims description 13
- 239000007790 solid phase Substances 0.000 claims description 13
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- 238000009835 boiling Methods 0.000 claims description 11
- 239000003575 carbonaceous material Substances 0.000 claims description 11
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 10
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 10
- 239000007772 electrode material Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 239000007791 liquid phase Substances 0.000 claims description 7
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 6
- 238000001994 activation Methods 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 6
- 239000001110 calcium chloride Substances 0.000 claims description 6
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 6
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 5
- 244000060011 Cocos nucifera Species 0.000 claims description 5
- 230000004913 activation Effects 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000005470 impregnation Methods 0.000 claims description 5
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 5
- 239000002808 molecular sieve Substances 0.000 claims description 5
- 239000001103 potassium chloride Substances 0.000 claims description 5
- 235000011164 potassium chloride Nutrition 0.000 claims description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 5
- 238000004108 freeze drying Methods 0.000 claims description 4
- 239000003507 refrigerant Substances 0.000 claims description 4
- 238000005096 rolling process Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 238000000354 decomposition reaction Methods 0.000 claims description 3
- 230000006698 induction Effects 0.000 claims description 3
- 239000013067 intermediate product Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000003801 milling Methods 0.000 claims 1
- 239000004576 sand Substances 0.000 claims 1
- 238000009792 diffusion process Methods 0.000 abstract description 4
- 239000011148 porous material Substances 0.000 description 15
- 238000012360 testing method Methods 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 239000010406 cathode material Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 5
- 230000002441 reversible effect Effects 0.000 description 5
- 150000004679 hydroxides Chemical class 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 239000002194 amorphous carbon material Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012163 sequencing technique Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides a porous carbon negative electrode material, a preparation method thereof, an electrode, a battery and a capacitor prepared from the porous carbon negative electrode material, and belongs to the technical field of battery negative electrode materials. Wherein, the raw materials for preparing the porous carbon negative electrode material are porous carbon and molten salt; the preparation method comprises the following steps: mixing porous carbon with molten salt, performing high-temperature treatment in an inert atmosphere, cooling, washing, separating and drying to obtain the porous carbon negative electrode material; the porous carbon negative electrode material prepared by the method has high ion capacity and high first charge-discharge efficiency as an electrode, and has a good ion diffusion channel, so that the porous carbon negative electrode material has high rate performance.
Description
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, an electrode prepared from the porous carbon cathode material, a battery prepared from the electrode, and a capacitor prepared from the electrode.
Background
The negative electrode materials used for the lithium ion battery at present are mainly modified natural graphite and artificial graphite, and the capacity of the graphite negative electrode material in the prior art is close to the theoretical value allowed by the structure, so that the bottleneck is faced to the continuous development of energy density, meanwhile, the capacity of the graphite in the sodium ion battery is too low to be practical, and the amorphous carbon material is considered as the negative electrode material which is beneficial to improving the energy and power density due to the structural absence of theoretical limitation, and is expected to be applied to the fields of lithium ion batteries, super capacitors, sodium ion batteries and the like.
The porous carbon material is thought to contribute to the improvement of the capacity for active ions and to exhibit a higher first capacity due to the abundant pore structure, however, the existing porous carbon material generally has the disadvantage of low first charge-discharge efficiency, the specific reason is not known at present, and generally thought to be related to large surface area and many defects, the first charge-discharge efficiency is low, which not only reduces the utilization rate of the negative electrode material, but also reduces the utilization rates of the positive electrode material and the electrolyte, thus being not beneficial to the improvement of energy density and the reduction of cost.
In the prior art, oxides, hydroxides or salts are also used for preparing the porous carbon material, but the introduction purposes are different, and the operation steps are different, so that the effect of the content of the invention cannot be obtained. For example, oxides and hydroxides generally have high melting points and cannot enter porous carbon channels in a liquid state to form supports for structures; although part of oxides and hydroxides with lower melting points can form liquid, the oxides and hydroxides have high reaction activity and cannot maintain the pore channel structure of the porous carbon; and part of the materials take salt as a pore-forming agent, the materials mainly play a role in the activation pore-forming process, and the temperature in the activation process is not enough to form a liquid supporting pore channel structure, and the effect of improving the first charge-discharge efficiency is not enough.
In order to improve the first charge-discharge efficiency of the porous carbon material, the material is generally treated by adopting a high-temperature inert atmosphere, the obtained material generally has a large platform capacity, the specific reason is not clear, the effect improvement is generally attributed to proper graphite interlayer spacing and a small pore diameter, but the platform capacity is easily influenced by a polarization effect during large-current discharge, and therefore the rate performance of the material is generally low.
Based on the above technical problems, there is a need for a porous carbon material with high rate capability while contributing to improvement of the first charge-discharge efficiency.
Disclosure of Invention
The invention aims to provide a porous carbon negative electrode material, a preparation method thereof, and an electrode, a battery and a capacitor prepared from the porous carbon negative electrode material, so as to solve the technical problem that the existing porous carbon material used as the negative electrode material generally has low first charge-discharge efficiency and rate capability.
In order to achieve the purpose, the invention provides a porous carbon negative electrode material, and the preparation raw materials of the porous carbon negative electrode material comprise porous carbon and molten salt.
The invention provides a preparation method of the porous carbon negative electrode material, which comprises the following steps: mixing porous carbon with molten salt, performing high-temperature treatment in an inert atmosphere, cooling, washing, separating and drying to obtain the porous carbon negative electrode material.
The inert atmosphere may be nitrogen or argon.
Further, the molten salt comprises one or more compounds with the melting point of less than or equal to 1000 ℃ and the boiling point of more than or equal to 1300 ℃; or the fused salt comprises one or more compounds with the melting point of less than or equal to 1000 ℃ and the boiling point of more than or equal to 1300 ℃ after decomposition or reaction.
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 of activation of the carbon-containing precursor.
Preferably, the porous carbon comprises one or more of coal-made activated carbon, coconut shell 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 equal volume impregnation or excess impregnation of the porous carbon after the molten salt is made into a solution.
Preferably, the solid phase mixing is one or a combination of two or more of rolling, ball milling or sanding the porous carbon and the molten salt.
More preferably, the mass ratio of the porous carbon to the molten salt 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 both of batch or continuous;
optionally, the high temperature treatment is one or a combination of internal heating or external heating;
optionally, the high temperature processing equipment comprises one or more of a rotary furnace, a tube furnace, a tunnel kiln or an induction furnace;
further, the temperature of the high-temperature treatment is 800-; the time of the high-temperature treatment is 0.1-10 h. The reason is that the high temperature is favorable for improving the first charge-discharge efficiency, and meanwhile, the porous carbon material pore channel structure is kept favorable for 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 heat up to 800-. The first stage of heating can melt the molten salt into the porous carbon pore channels; the porous carbon can obtain high rate performance by the second section of heating, and the high-temperature treatment process can obtain better effect by the two sections of heating.
In the preparation method, optionally, the cooling is one or the combination of natural cooling or refrigerant forced cooling;
optionally, the washing is one or a combination of water washing, solvent washing or supercritical washing;
optionally, the separation is one or a combination of filtration or centrifugation;
optionally, the drying is one or more of vacuum drying, heat drying or freeze drying.
An electrode material comprises the porous carbon negative electrode material.
A battery comprising the electrode material.
A capacitor comprises the electrode material.
According to the invention, porous carbon and fused salt are mixed and then subjected to a series of treatments to change the structure of the porous carbon to obtain the porous carbon cathode material, and the fused salt is converted into a liquid state at a certain temperature, enters the porous carbon pore passage, and supports the pore structure of the material in the subsequent treatment process at a higher temperature, so that the ion capacity and the first charge-discharge efficiency are improved, and the porous carbon cathode material also has a good ion diffusion passage and high multiplying power performance; the negative electrode material of the battery obtained by adopting the porous carbon negative electrode material has excellent first charge-discharge efficiency and rate capability, and can improve the utilization rate of the positive electrode material, the negative electrode material and the electrolyte and reduce the cost.
Detailed Description
The terms as used herein:
"prepared from … …" is synonymous with "comprising". As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having," "contains" or any other variation thereof, 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 the parts by mass of the component A are a parts and the parts by mass of the component B are B parts, the mass ratio of the component A to the component B is expressed as 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 embodiment of the invention provides a porous carbon negative electrode material, a preparation method of the porous carbon negative electrode material, an electrode prepared from the porous carbon negative electrode material, a battery and a capacitor, wherein the preparation method of the porous carbon negative electrode material comprises the following steps: mixing porous carbon with molten salt, carrying out high-temperature treatment under an inert atmosphere, cooling, washing, separating and drying to obtain the porous carbon negative electrode material. Wherein the molten salt comprises one or more compounds with the melting point of less than or equal to 1000 ℃ and the boiling point of more than or equal to 1300 ℃; or the fused salt comprises one or more compounds of which the melting point is less than or equal to 1000 ℃ and the boiling point is more than or equal to 1300 ℃ after decomposition or reaction. 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 of activation of 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-made active carbon, coconut shell active carbon, active carbon fiber and carbon molecular sieve.
The embodiment of the invention mixes the porous carbon with the molten salt, and the mixing is liquid phase mixing or solid phase mixing. As a preferred example, the liquid phase mixing is to impregnate the porous carbon with equal volume or in excess after preparing the molten salt into a solution; the solid phase mixing is one or more of rolling, ball milling or sanding 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. The sodium chloride and the potassium chloride are not limited by the mixing mode, and the magnesium chloride and the calcium chloride are not suitable for liquid phase mixing, and 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 a batch type or a continuous type; the high-temperature treatment is one or the combination 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 time of the high-temperature treatment is 0.1-10 h; the temperature of the high-temperature treatment is 800-1800 ℃.
As a more preferable embodiment, the high temperature treatment is to heat up to 800-1000 ℃ for reaction for 0.1-2h, and then heat up to 1300-1800 ℃ for residence time for 0.5-8 h.
The molten salt is converted into a liquid state at high temperature, enters the porous carbon pore channel, and supports the pore structure of the material in the subsequent higher-temperature treatment process, so that the porous carbon material has high ion capacity and high first charge-discharge efficiency, and also has a good ion diffusion channel, thereby having high multiplying power performance.
In the embodiment of the invention, the cooling is one or the combination of natural cooling or refrigerant forced cooling; the washing is one or combination of water washing, solvent washing or supercritical washing; the separation is one or a combination of filtration and centrifugation; the drying is one or more of vacuum drying, heating drying or freeze drying.
In the embodiment of the invention, the carbon content of the porous carbon negative electrode material is more than 98 percent, and N is2The specific surface area is more than 300m2The ratio of micropores is more than 80%, and the pore volume of micropores is more than 0.6cm3/g。
The embodiment of the invention also provides an electrode material which comprises the porous carbon negative electrode material. The electrode containing the porous carbon negative electrode material and other auxiliary components are a binder, a conductive agent and the like which are well known by the technical personnel.
The embodiment of the invention also provides a battery comprising the electrode material. Other parts of the battery including the above-described electrode include a positive electrode, a separator, an electrolyte, additives, and the like, which are well known to those skilled in the art.
The embodiment of the invention also provides a capacitor comprising the electrode material. The other parts of the capacitor including the above electrodes include an electrolyte, a separator, 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 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
The embodiment provides a preparation method of a porous carbon negative electrode material, which comprises the following steps: mixing sodium chloride (melting point 801 ℃, boiling point 1413 ℃) with coal-made active carbon liquid (excessive impregnation of coal-made active carbon after preparing sodium chloride into solution), performing high-temperature treatment by adopting a tube furnace under inert atmosphere at 1000 ℃ for 10 hours, naturally cooling, washing with water, filtering, and drying in vacuum at 80 ℃ to obtain the porous carbon negative electrode material.
The test shows that the carbon content of the obtained porous carbon negative electrode material is 98.3 percent, and N is2The specific surface area is 320m2G, the proportion of micropores is 85%, and the pore volume of the micropores is 0.63cm3/g。
The porous carbon negative electrode material is used as a negative electrode of a CR2032 battery assembled by using a sodium metal sheet as a counter electrode and using 1M NaPF6-EC/DMC (1:1v/v) as an electrolyte, and the negative electrode has the first reversible capacity of 455mah/g, the first charge-discharge efficiency of 89 percent and the 0.5C/0.2C of 85 percent through tests.
Example 2
The embodiment provides a preparation method of a porous carbon negative electrode material, which comprises the following steps: the preparation method comprises the steps of mixing potassium chloride (melting point 770 ℃ and boiling point 1420 ℃) and coconut shell activated carbon in a ratio of 3:1 through rolling and solid phase mixing, performing high-temperature treatment by adopting a rotary heating furnace under inert atmosphere at 1350 ℃ for 5 hours, then performing water washing after forcibly cooling a refrigerant, performing centrifugal separation, and performing vacuum drying at 80 ℃ to obtain the porous carbon cathode material.
The carbon content of the obtained porous carbon negative electrode material is 98.8 percent through analysis and test, and N is2The specific surface area is 330m2(ii)/g, the ratio of micropores was 87%, and the pore volume of micropores was 0.67cm3/g。
The porous carbon negative electrode material is used as a negative electrode of a CR2032 battery assembled by using a sodium metal sheet as a counter electrode and using 1M NaPF6-EC/DMC (1:1v/v) as an electrolyte, and the negative electrode has the first reversible capacity of 460mah/g, the first charge-discharge efficiency of 90 percent and the first charge-discharge efficiency of 85.3 percent at 0.5C/0.2C through tests.
Example 3
The embodiment provides a preparation method of a porous carbon negative electrode material, which comprises the following steps: mixing magnesium chloride (melting point 714 ℃, boiling point 1412 ℃) and a carbon molecular sieve in a ratio of 4:1 by ball milling solid phase, performing high-temperature treatment at 1400 ℃ for 1h in an inert atmosphere by using a rotary heating furnace, then naturally cooling, washing with water, filtering, and freeze-drying at 80 ℃ to obtain the porous carbon negative electrode material.
The analysis and test show that the carbon content of the obtained porous carbon negative electrode material is 99 percent, and N2The specific surface area is 350m2(89%) of micropores, and a micropore volume of 0.72cm3/g。
The porous carbon negative electrode material is used as a negative electrode of a CR2032 battery which is assembled by taking a sodium metal sheet as a counter electrode and taking 1M NaPF6-EC/DMC (1:1v/v) as electrolyte, and the negative electrode 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 at 0.5C/0.2C through tests.
Example 4
The embodiment provides a preparation method of a porous carbon negative electrode material, which comprises the following steps: mixing calcium chloride (melting point 782 ℃ and boiling point more than 1600 ℃) and activated carbon fiber in a ratio of 6:1 by ball milling and solid phase mixing, performing high-temperature treatment at 1580 ℃ for 8 hours by using a rotary heating furnace in an inert atmosphere, naturally cooling, washing with water, filtering, and drying in vacuum at 80 ℃ to obtain the porous carbon cathode material.
The carbon content of the obtained porous carbon negative electrode material is 98 percent through analysis and test, and N is2The specific surface area is 337m2(ii)/g, the ratio of micropores was 87%, and the pore volume of micropores was 0.69cm3/g。
The porous carbon negative electrode material is used as a negative electrode of a CR2032 battery which is assembled by taking a sodium metal sheet as a counter electrode and taking 1M NaPF6-EC/DMC (1:1v/v) as electrolyte, and the negative electrode 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 at 0.5C/0.2C through tests.
Example 5
The embodiment provides a preparation method of a porous carbon negative electrode material, which comprises the following steps: mixing calcium chloride (melting point 782 ℃ and boiling point above 1600 ℃) and activated carbon fiber in a ratio of 10:1 by ball milling and solid phase mixing, heating to 900 ℃ by adopting a rotary heating furnace under inert atmosphere, reacting for 1h, then heating to 1800 ℃ and staying for 3 h. And then naturally cooling, washing with water, filtering, and drying in vacuum at 80 ℃ to obtain the porous carbon negative electrode material.
The carbon content of the obtained porous carbon negative electrode material is 99 percent through analysis and test, and N is2The specific surface area is 423m2The ratio of micropores to the total volume of the solution is 90%, and the pore volume of the micropores is 0.68cm3/g。
The porous carbon negative electrode material is used as a negative electrode of a CR2032 battery assembled by taking a sodium metal sheet as a counter electrode and 1M NaPF6-EC/DMC (1:1v/v) as electrolyte, and tests show that the porous carbon negative electrode material has a first reversible capacity of 485mah/g, the first charge-discharge efficiency is 95%, and the 0.5C/0.2C is 88%.
Based on the above exemplary embodiments extracted from the experimental data, it can be seen that for the porous carbon, the performance of the obtained porous carbon anode material is, from low to high, in order: coal-based activated carbon, coconut shell activated carbon, carbon molecular sieve and activated carbon fiber. The higher the temperature within the operating range, the better the performance with respect to temperature. For the ratio of the molten salt to the activated carbon, the ratio of the molten salt required by different types of activated carbon is different, and the method can be generally referred to the sequencing of porous carbon raw materials, when the consumption 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 amount of the molten salt is insufficient, the structure of the activated carbon partially collapses, and the performance is reduced.
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 porous carbon negative electrode material is characterized in that raw materials for preparing the porous carbon negative electrode material comprise porous carbon and molten salt.
2. The preparation method of the porous carbon negative electrode material of claim 1, characterized by mixing porous carbon with molten salt, performing high-temperature treatment in an inert atmosphere, cooling, washing, separating, and drying to obtain the porous carbon negative electrode material.
3. The method according to claim 2, wherein the molten salt comprises one or more compounds having a melting point of 1000 ℃ or less and a boiling point of 1300 ℃ or more; or the fused salt comprises one or more compounds of which the melting point is less than or equal to 1000 ℃ and the boiling point is more than or equal to 1300 ℃ after decomposition or reaction;
preferably, the molten salt comprises one or more of sodium chloride, potassium chloride, magnesium chloride or calcium chloride.
4. The production method according to claim 2, wherein the porous carbon comprises one or more of a carbon material obtained by physical or chemical activation of a carbon-containing precursor, an intermediate product of activation of a carbon-containing precursor;
preferably, the porous carbon comprises one or more of coal-made activated carbon, coconut shell activated carbon, activated carbon fiber and carbon molecular sieve.
5. The production method according to claim 2, wherein the porous carbon is mixed with a molten salt, the mixing being liquid-phase mixing or solid-phase mixing;
preferably, the liquid phase mixing is to prepare a molten salt into a solution and perform equal-volume impregnation or excessive impregnation on the porous carbon;
preferably, the solid phase mixing is one or more of rolling, ball milling or sand milling the porous carbon and the molten salt;
more preferably, the mass ratio of the porous carbon to the molten salt in the solid-phase mixing is 1:10 to 10: 1.
6. The method of claim 2, wherein the high temperature treatment satisfies one or more of the following conditions:
a. the high-temperature treatment is one or the combination of a batch type or a continuous type;
b. the high-temperature treatment is one or the combination of internal heating or external heating;
c. the high-temperature treatment equipment comprises one or more of a rotary heating furnace, a tube furnace, a tunnel kiln or an induction furnace;
d. the temperature of the high-temperature treatment is 800-1800 ℃, and the time of the high-temperature treatment is 0.1-10 h;
preferably, the high temperature treatment is to heat up to 800-.
7. The method of claim 2, further satisfying one or more of the following conditions:
e. the cooling is one or the combination of natural cooling or refrigerant forced cooling;
f. the washing is one or combination of water washing, solvent washing or supercritical washing;
g. the separation is one or a combination of filtration and centrifugation;
h. the drying is one or more of vacuum drying, heating drying or freeze drying.
8. An electrode material comprising the porous carbon negative electrode material according to claim 1.
9. A battery comprising the electrode material according to claim 8.
10. A capacitor comprising the electrode material according to claim 8.
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