CN112194126A - Preparation method of lithium ion battery cathode porous carbon material - Google Patents

Preparation method of lithium ion battery cathode porous carbon material Download PDF

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Publication number
CN112194126A
CN112194126A CN202011100013.8A CN202011100013A CN112194126A CN 112194126 A CN112194126 A CN 112194126A CN 202011100013 A CN202011100013 A CN 202011100013A CN 112194126 A CN112194126 A CN 112194126A
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China
Prior art keywords
carbon material
template
porous carbon
lithium ion
ion battery
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CN202011100013.8A
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Chinese (zh)
Inventor
曹曦
刘明义
朱勇
徐若晨
曹传钊
郑建涛
李晴
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Huaneng Clean Energy Research Institute
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Huaneng Clean Energy Research Institute
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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
    • 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
    • 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
    • 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
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a preparation method of a lithium ion battery cathode porous carbon material, which takes an organic matter as a carbon source, adopts water-soluble salt as a template, carries out high-temperature carbonization in an inert atmosphere, and removes the template by washing to form a porous structure; adding alkali as a catalyst, performing catalytic pore-forming in a high-temperature carbonization process, removing residual impurities by acid washing, further expanding pores and forming a microporous structure to construct a porous carbon material with a micro-meso-macroporous structure, wherein a large number of micropores provide embedding positions for lithium ions, so that the charging and discharging capacity of the porous carbon material is improved, mesopores with slightly larger pore diameters are used as fast transmission channels for the lithium ions to enter the carbon material, and macropores can be used as ion buffer storages to buffer during high-rate charging and discharging. And the carbon material has wide carbon source, the water-soluble template is easy to remove, and the water-soluble template can be repeatedly used.

Description

Preparation method of lithium ion battery cathode porous carbon material
Technical Field
The invention relates to the field of battery materials, in particular to a preparation method of a lithium ion battery cathode porous carbon material.
Background
The lithium ion battery mainly comprises a positive electrode material, a negative electrode material, an electrolyte and a diaphragm, wherein when the lithium ion battery is charged and lithium ions are charged, the lithium ions are transferred from the lithium-rich positive electrode material (generally a multi-element lithium-rich compound, such as lithium cobaltate, lithium iron phosphate and the like) to the negative electrode material (a lithium material capable of being de-intercalated and de-intercalated), and the lithium ions are de-intercalated and de-intercalated. Similarly, when the battery is discharged, lithium ions are transferred from the negative electrode material to the positive electrode material, and the state is restored to the uncharged state. Since lithium ions are transferred back and forth between the positive and negative electrodes during charging and discharging, lithium ion batteries are also commonly referred to as rocking chair batteries.
In addition to the requirement of high reversible specific capacity, the selection of the negative electrode material has important factors for investigation, such as the lithium intercalation potential, the volume change rate in the lithium deintercalation process, the conductivity and the cost thereof. Alloying materials such as simple substance silicon, tin, germanium and the like can be formed, the volume change is large in the charging and discharging process, the cycle performance is poor, a special nano structure is often needed as a buffer, the preparation method is complex, and the cost is high. The graphite material which is commercially used at present has a low theoretical capacity (only 372mAh/g) and is difficult to meet the requirement of increasing the energy density of the battery, so that the development of a novel negative electrode material becomes one of the hot spots of the current research.
Disclosure of Invention
In order to overcome the defects of low capacity, difficult preparation, high cost and poor cycle stability of the conventional negative electrode material, the invention aims to provide a preparation method of a porous carbon material for a negative electrode of a lithium battery, which has high reversible capacity and low cost and is suitable for large-current charge and discharge.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a lithium ion battery cathode porous carbon material comprises the following steps:
1) preparing a carbon source solution with the mass concentration of 10% -50% by using a carbon-containing organic substance and deionized water, and fully mixing the carbon source solution with water-soluble salt serving as a template, drying and grinding to obtain a mixture A; the mass ratio of the carbon-containing organic matter to the template is 1:10-2: 1;
2) carbonizing the mixture A at high temperature in an inert atmosphere to obtain a product B;
3) washing the product B with water to remove the template, and then drying to obtain a product C;
4) adding alkali serving as a catalyst into the product C, and fully mixing the product C and the alkali catalyst in a mass ratio of 10:1-1:2 to obtain a mixture D;
5) carbonizing the mixture D at high temperature in an inert atmosphere to obtain a product E;
6) and adding a dilute acid solution into the product E to remove residual impurities, washing with water and drying to obtain the lithium ion battery cathode porous carbon material F with micropores, mesopores and macropores.
Further, the organic matter containing carbon is phenolic resin, glucose, sucrose or polyvinyl alcohol.
Further, the template is NaCl and Na2SO4Or MgSO 24。
Further, the carbonization conditions in the step 2) are as follows: inert atmosphere is N2Or Ar or the mixed gas of the Ar and the Ar, wherein the carbonization temperature is 500-700 ℃, and the carbonization time is 1-2 hours; the carbonization conditions of the step 5) are as follows: inert atmosphere is N2Or Ar or the mixed gas of the Ar and the Ar, the carbonization temperature is 600-900 ℃, and the carbonization time is 1-3 hours.
Further, the catalyst is NaOH or KOH.
Further, the dilute acid solution is HNO3A mixture of one or more of a solution, a HCl solution, and an acetic acid solution.
Compared with the prior art, the invention has the following beneficial technical effects:
after the soluble salt is fully mixed with the carbon source solution and dried, the soluble salt can be crystallized to form nano particles with different sizes, in the further carbonization process, the salt nano particles can not be decomposed, and the carbon source is carbonized on the surfaces of the nano particles. And after the nanoparticle template is removed by subsequent water washing, the position of the template is converted into a nanometer pore channel. And activating by using alkali as a catalyst, so that the size of the nanometer pore channel can be further enlarged to form a mesopore and a macropore. Meanwhile, the catalyst can be activated on the surface of the carbon material to generate a large number of micropores, and finally the carbon material with a micro-meso-macroporous structure is formed, wherein the large number of micropores can provide a large number of active sites for lithium ion intercalation and deintercalation, mesopores with slightly larger pore diameters are used as fast transmission channels for lithium ions to enter the interior of the carbon material, and simultaneously provide larger capacitance capacity, and the macropores can provide buffer for ion transmission during high-rate charge and discharge. The preparation method has the advantages of wide carbon source, easy removal of the water-soluble template, repeated use, simple integral preparation process of the carbon material and low cost.
Drawings
FIG. 1 is a process flow diagram of the present invention; wherein 1 is a carbon source solution, 2 is a water-soluble salt, 3 is a mixture A, 4 is a product B, 5 is a template solution, 6 is a product C, 7 is a catalyst, 8 is a mixture D, 9 is a product E, 10 is a dilute acid solution, and 11 is a lithium ion battery cathode porous carbon material.
FIG. 2 is a schematic structural view of the present invention; wherein a is macropore, b is mesopore, and c is micropore.
Detailed Description
Embodiments of the invention are described in further detail below:
referring to fig. 1, in the preparation process, a carbon-containing organic solution is used as a carbon source solution 1, the mass concentration of the carbon source solution is 10% -50%, a water-soluble salt 2 is used as a template, the mixture is fully mixed, dried and ground to obtain a mixture A3, the mass ratio of the carbon-containing organic matter to the template is 1:10-2:1, the mixture is carbonized at a high temperature in an inert atmosphere to obtain a product 4, the product 4 is washed with water to remove the template, the obtained liquid is used as a template solution 5, and the obtained solid is dried to obtain a product C6; adding an alkali catalyst 7 into the product C6, wherein the mass ratio of the product C to the alkali catalyst is 10:1-1:2, further grinding and mixing to obtain a mixture D8, then carbonizing at high temperature in an inert atmosphere, catalytically forming pores, further expanding pores and forming a product E9; and then adding a dilute acid solution 10 to remove residual impurities, thereby obtaining the lithium ion battery cathode porous carbon material 11 with a microporous c, mesoporous b and macroporous a multilevel pore channel structure.
Among these, carbon-containing organic materials include, but are not limited to, for example, phenolic resins, glucose, sucrose, and polyvinyl alcohol; templates include but are not limited to NaCl, Na2SO4、MgSO4Etc.; catalyst bases include, but are not limited to, such as NaOH, KOH; inert atmosphere is N2Or Ar, or a mixed gas of the two. The carbonization is carried out in two steps, wherein the temperature of the first step is 500-700 ℃, and the carbonization time is 1-2 hours; the second step is at the temperature of 600-; dilute acid solutions for catalyst impurity removal include, but are not limited to, HNO3Solutions, HCl solutions, acetic acid solutions, etc., or mixed acid solutions of various acids.
The present invention is described in further detail below with reference to examples:
example 1
Preparing a carbon source solution with the mass concentration of 30% by taking soluble phenolic resin as a carbon source, adding a NaCl template according to the ratio of an organic carbon source to the template of 1:10, fully mixing, drying and grinding. N is a radical of2Carbonizing for 1h at 500 ℃ under the protection of inert atmosphere, cooling, washing with water, and removing the template; drying the obtained product, adding NaOH as an alkali catalyst according to the mass ratio of 10:1, mixing, and continuing to add N2Carbonizing at 600 deg.C for 1h under the protection of inert atmosphere, and adding diluted HNO3After sufficient washing, washing with water and drying to obtain the final porous carbon sample 1.
Example 2
Glucose is used as a carbon source to prepare a carbon source solution with the mass concentration of 50 percent, and Na is added according to the ratio of the organic carbon source to the template of 2:12SO4Template, mixing, baking and grinding. Under the protection of Ar inert atmosphere,carbonizing for 2h at 700 ℃, cooling, washing with water, and removing the template; and drying the obtained product, adding KOH as an alkali catalyst according to the mass ratio of 1:2, mixing, continuously carbonizing for 3h at 900 ℃ under the protection of Ar inert atmosphere, fully washing with diluted HCl, washing with water and drying to obtain a final porous carbon sample 2.
Example 3
Using sucrose as a carbon source to prepare a carbon source solution with the mass concentration of 10%, and adding MgSO (MgSO) according to the ratio of the organic carbon source to the template of 1:14Template, mixing, baking and grinding. N is a radical of2Carbonizing at 600 ℃ for 1.5h under the protection of a 50%/50% mixed inert atmosphere, cooling, washing with water, and removing the template; drying the obtained product, adding NaOH as an alkali catalyst according to the mass ratio of 10:1, mixing, and continuing to add N2And carbonizing the mixture of/Ar (50%/50%) for 2 hours at 800 ℃ under the protection of mixed inert atmosphere, fully washing the carbonized mixture by using acetic acid, and washing and drying the carbonized mixture to obtain a final porous carbon sample 3.
Example 4
Preparing carbon source solution with the mass concentration of 50% by taking polyvinyl alcohol as a carbon source, adding a NaCl template according to the ratio of the organic carbon source to the template of 2:1, fully mixing, drying and grinding. N is a radical of2Carbonizing for 2h at 700 ℃ under the protection of inert atmosphere, cooling, washing with water, and removing the template; drying the obtained product, adding KOH as an alkali catalyst according to the mass ratio of 1:2, mixing, and continuing to add N2Carbonizing at 900 ℃ for 3h under the protection of inert atmosphere, fully washing with mixed acid (10% HCl + 10% acetic acid), washing with water and drying to obtain a final porous carbon sample 4.
The present invention has been described in order to facilitate the understanding of the present invention, but the embodiments of the present invention are not limited to the above-described examples, and any changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit of the present invention should be construed as being equivalent substitutions within the scope of the present invention.

Claims (6)

1. A preparation method of a lithium ion battery cathode porous carbon material is characterized by comprising the following steps:
1) preparing a carbon source solution with the mass concentration of 10% -50% by using a carbon-containing organic substance and deionized water, and fully mixing the carbon source solution with water-soluble salt serving as a template, drying and grinding to obtain a mixture A; the mass ratio of the carbon-containing organic matter to the template is 1:10-2: 1;
2) carbonizing the mixture A at high temperature in an inert atmosphere to obtain a product B;
3) washing the product B with water to remove the template, and then drying to obtain a product C;
4) adding alkali serving as a catalyst into the product C, and fully mixing the product C and the alkali catalyst in a mass ratio of 10:1-1:2 to obtain a mixture D;
5) carbonizing the mixture D at high temperature in an inert atmosphere to obtain a product E;
6) and adding a dilute acid solution into the product E to remove residual impurities, washing with water and drying to obtain the lithium ion battery cathode porous carbon material F with micropores, mesopores and macropores.
2. The method for preparing the porous carbon material for the negative electrode of the lithium ion battery according to claim 1, wherein the carbon-containing organic substance is phenolic resin, glucose, sucrose or polyvinyl alcohol.
3. The method for preparing the porous carbon material for the negative electrode of the lithium ion battery according to claim 1, wherein the template is NaCl or Na2SO4Or MgSO 24。
4. The preparation method of the lithium ion battery negative electrode porous carbon material according to claim 1, wherein the carbonization conditions in the step 2) are as follows: inert atmosphere is N2Or Ar or the mixed gas of the Ar and the Ar, wherein the carbonization temperature is 500-700 ℃, and the carbonization time is 1-2 hours; the carbonization conditions of the step 5) are as follows: inert atmosphere is N2Or Ar or the mixed gas of the Ar and the Ar, the carbonization temperature is 600-900 ℃, and the carbonization time is 1-3 hours.
5. The method for preparing the lithium ion battery negative electrode porous carbon material according to claim 1, wherein the catalyst is NaOH or KOH.
6. The method for preparing the porous carbon material for the negative electrode of the lithium ion battery according to claim 1, wherein the dilute acid solution is HNO3A mixture of one or more of a solution, a HCl solution, and an acetic acid solution.
CN202011100013.8A 2020-10-14 2020-10-14 Preparation method of lithium ion battery cathode porous carbon material Pending CN112194126A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114620722A (en) * 2022-03-17 2022-06-14 青岛华世洁环保科技有限公司 Porous carbon negative electrode material, preparation method thereof, electrode, battery and capacitor prepared from porous carbon negative electrode material
KR20220150138A (en) * 2021-05-03 2022-11-10 서울대학교산학협력단 Carbon sheet and porous catalyst comprising the same

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110304629A (en) * 2018-03-25 2019-10-08 北京金羽新能科技有限公司 A kind of classifying porous Carbon Materials and its supercapacitor of preparation
CN111039289A (en) * 2019-12-20 2020-04-21 中南民族大学 Preparation method of alkali-activated porous carbon and application of alkali-activated porous carbon in adsorption of toluene in liquid paraffin

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110304629A (en) * 2018-03-25 2019-10-08 北京金羽新能科技有限公司 A kind of classifying porous Carbon Materials and its supercapacitor of preparation
CN111039289A (en) * 2019-12-20 2020-04-21 中南民族大学 Preparation method of alkali-activated porous carbon and application of alkali-activated porous carbon in adsorption of toluene in liquid paraffin

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20220150138A (en) * 2021-05-03 2022-11-10 서울대학교산학협력단 Carbon sheet and porous catalyst comprising the same
KR102568154B1 (en) * 2021-05-03 2023-08-18 서울대학교산학협력단 Carbon sheet and porous catalyst comprising the same
CN114620722A (en) * 2022-03-17 2022-06-14 青岛华世洁环保科技有限公司 Porous carbon negative electrode material, preparation method thereof, electrode, battery and capacitor prepared from porous carbon negative electrode material
CN114620722B (en) * 2022-03-17 2023-09-19 青岛华世洁环保科技有限公司 Porous carbon negative electrode material, preparation method thereof, electrode, battery and capacitor prepared from porous carbon negative electrode material

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