CN105845936B - Preparation method of modified hard carbon negative electrode material for lithium ion battery - Google Patents
Preparation method of modified hard carbon negative electrode material for lithium ion battery Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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- 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 modified hard carbon negative electrode material for a lithium ion battery, which comprises the following steps: 1) firstly, adding phenol and strong base into a formaldehyde solution or an acetaldehyde solution to obtain a water-soluble phenolic resin; 2) adding ammonium persulfate into the water-soluble phenolic resin prepared in the step 1), adding vegetable oil with the same volume after completely dissolving, uniformly mixing, and pouring into a hydrothermal reaction kettle for reaction to obtain a solid hard carbon precursor; 3) under the protection of nitrogen or inert gas, heating the solid hard carbon precursor obtained in the step 2) to obtain hard carbon; 4) carrying out ball milling or crushing on the hard carbon; 5) and adding a carbon source into the hard carbon matrix, uniformly mixing, and carrying out heat preservation and heating to obtain the modified hard carbon negative electrode material for the lithium ion battery. The modified hard carbon negative electrode material has excellent electrochemical performance and excellent lithium intercalation and lithium deintercalation capabilities, the first discharge specific capacity is more than 400mAh/g, in the best embodiment, the first discharge specific capacity is 503mAh/g, the first charge and discharge efficiency is as high as 94.5%, and the modified hard carbon negative electrode material is suitable for power and energy storage lithium ion batteries.
Description
Technical Field
The invention relates to the technical field of electrodes, and particularly provides a preparation method of a modified hard carbon negative electrode material for a lithium ion battery.
Background
With the continuous deepening of global energy crisis, the gradual depletion of petroleum resources, the aggravation of atmospheric pollution and global temperature rise, and the development of clean energy is imperative. In the development of new energy, the lithium ion battery with the advantages of high working voltage, high energy density, stable discharge voltage, long cycle life, environmental friendliness and the like is widely applied. The cathode material is one of the key factors for evaluating the comprehensive performance of the lithium ion battery. The lithium battery cathode material which is commercially used at present is mainly graphite, and the graphite material has a high-degree of graphitization and a high-layered structure, so that the lithium intercalation capacity under heavy-current charging and discharging is low. With the development of social productivity and the continuous progress of science and technology, lithium ion batteries using hard carbon as the negative electrode material are more suitable for use under large current charging and discharging due to the special structure of the hard carbon negative electrode material, and are receiving attention. Compared with graphite, hard carbon also has the characteristic of good compatibility with electrolyte (especially PC electrolyte). However, the problems of high electrode potential, potential lag and low first efficiency are still not effectively solved.
Disclosure of Invention
In view of the above, the present invention provides a method for preparing a modified hard carbon negative electrode material for a lithium ion battery, which has high capacity, high charge-discharge efficiency and high rate charge-discharge performance.
In order to achieve the purpose, the invention adopts the following technical scheme: a preparation method of a modified hard carbon negative electrode material for a lithium ion battery comprises the following steps:
1) firstly, adding phenol and strong base into a formaldehyde solution or an acetaldehyde solution, and stirring and reacting for 5-12h at the temperature of 50-80 ℃ to obtain water-soluble phenolic resin;
2) adding ammonium persulfate into the water-soluble phenolic resin prepared in the step 1), after completely dissolving, adding vegetable oil with the same volume, uniformly mixing, pouring into a hydrothermal reaction kettle, placing into a microwave oven with the power of 600-2000 w, heating for 10-600 s, filtering after the reaction is finished, washing for 3-10 times with water and ethanol, and drying at the temperature of 40 ℃ to obtain a solid hard carbon precursor;
3) under the protection of nitrogen or inert gas, heating the solid hard carbon precursor obtained in the step 2) to 400 ℃ at the heating rate of 1-5 ℃/min, preserving heat for 1h, then heating to 500-1200 ℃ at the heating rate of 0.5-3 ℃/min, preserving heat for 3-20h, and then naturally cooling to room temperature to obtain a hard carbon matrix;
4) carrying out ball milling or crushing on the hard carbon to obtain a hard carbon matrix with the granularity of 1-60 mu m;
5) adding a carbon source into a hard carbon matrix, uniformly mixing at the rotation speed of 500-3500r/min for 15-120min, heating to 400 ℃ at the heating speed of 2-5 ℃/min under the protection of nitrogen or inert gas, preserving heat for 1h, heating to 500-1200 ℃ at the heating speed of 0.5-3 ℃/min, preserving heat for 7-10h, and naturally cooling to room temperature to obtain the modified hard carbon cathode material for the lithium ion battery.
As a preferable scheme, in the step 1), the formaldehyde solution or the acetaldehyde solution is: phenol: strong base 1: 2: 0.05 to 0.2.
As a preferable scheme, the mass (g) of ammonium persulfate in the step 2) is as follows: the volume (mL) of the water-soluble phenolic resin is 1: 10-50.
Preferably, the concentration of the formaldehyde solution is 37%, and the concentration of the acetaldehyde solution is 40%.
Preferably, the strong base is at least one of NaOH and KOH, and the purity is more than 99.9%.
Preferably, the purity of the ammonium persulfate is more than 99.9%.
As a preferred embodiment, the vegetable oil is at least one of sesame oil, rapeseed oil, or olive oil.
As a preferable scheme, the carbon source in step 5) is at least one of petroleum asphalt, coal asphalt and coal tar.
Compared with the prior art, the invention has obvious advantages and beneficial effects, and specifically comprises the following steps: the modified hard carbon negative electrode material has excellent electrochemical performance and excellent lithium intercalation and lithium deintercalation capabilities, the first discharge specific capacity is more than 400mAh/g, in the best embodiment, the first discharge specific capacity is up to 497mAh/g, the first charge and discharge efficiency is up to 92 percent, and the modified hard carbon negative electrode material is suitable for power and energy storage lithium ion batteries; the preparation method is simple and easy to implement, has low cost and can be applied to industrial production.
Detailed Description
Example 1
A preparation method of a modified hard carbon negative electrode material for a lithium ion battery comprises the following steps:
1) firstly, adding phenol and strong base into a formaldehyde solution, and stirring and reacting for 5 hours at the temperature of 80 ℃ to obtain water-soluble phenolic resin; according to the mass ratio, the formaldehyde solution: phenol: strong base 1: 2: 0.2; the concentration of the formaldehyde solution is 37 percent; the strong base is NaOH, and the purity is more than 99.9%.
2) Adding ammonium persulfate into the water-soluble phenolic resin prepared in the step 1), wherein the mass (g) of the ammonium persulfate is as follows: after the water-soluble phenolic resin is completely dissolved, adding vegetable oil with the same volume, uniformly mixing, pouring into a hydrothermal reaction kettle, placing into a microwave oven with the power of 2000w, heating for 10s, filtering after the reaction is finished, washing for 10 times by using water and ethanol, and drying at the temperature of 40 ℃ to obtain a solid hard carbon precursor; the purity of the ammonium persulfate is more than 99.9 percent; the vegetable oil is sesame oil.
3) Under the protection of nitrogen or inert gas, heating the solid hard carbon precursor obtained in the step 2) to 400 ℃ at a heating rate of 5 ℃/min, preserving heat for 1h, then heating to 500 ℃ at a heating rate of 3 ℃/min, preserving heat for 20h, and then naturally cooling to room temperature to obtain a hard carbon matrix;
4) carrying out ball milling or crushing on the hard carbon to obtain a hard carbon matrix with the granularity of 1-60 mu m;
5) adding a carbon source into a hard carbon matrix, uniformly mixing, heating to 400 ℃ at a rotation speed of 3500r/min for 15min under the protection of nitrogen or inert gas, keeping the temperature for 1h, heating to 1200 ℃ at a heating speed of 3 ℃/min, keeping the temperature for 7h, and naturally cooling to room temperature to obtain the modified hard carbon negative electrode material for the lithium ion battery; the carbon source is petroleum asphalt.
Example 2
A preparation method of a modified hard carbon negative electrode material for a lithium ion battery comprises the following steps:
1) firstly, adding phenol and strong base into an acetaldehyde solution, and stirring and reacting at the temperature of 50 ℃ for 12 hours to obtain water-soluble phenolic resin; the mass ratio of the formaldehyde solution or the acetaldehyde solution is as follows: phenol: strong base 1: 2: 0.05; the concentration of the acetaldehyde solution is 40 percent; the strong base is KOH, and the purity is more than 99.9 percent.
2) Adding ammonium persulfate into the water-soluble phenolic resin prepared in the step 1), wherein the mass (g) of the ammonium persulfate is as follows: after the water-soluble phenolic resin is completely dissolved, adding vegetable oil with the same volume, uniformly mixing, pouring into a hydrothermal reaction kettle, placing into a microwave oven with the power of 600w, heating for 600s, filtering after the reaction is finished, washing for 3 times by using water and ethanol, and drying at the temperature of 40 ℃ to obtain a solid hard carbon precursor; the purity of the ammonium persulfate is more than 99.9 percent; the vegetable oil is rapeseed oil.
3) Under the protection of nitrogen or inert gas, heating the solid hard carbon precursor obtained in the step 2) to 400 ℃ at a heating rate of 1 ℃/min, preserving heat for 1h, then heating to 500 ℃ at a heating rate of 0.5 ℃/min, preserving heat for 20h, and then naturally cooling to room temperature to obtain a hard carbon matrix;
4) carrying out ball milling or crushing on the hard carbon to obtain a hard carbon matrix with the granularity of 1-60 mu m;
5) adding a carbon source into a hard carbon matrix, uniformly mixing, heating to 400 ℃ at a speed of 500r/min for 120min under the protection of nitrogen or inert gas, preserving heat for 1h at a heating speed of 2 ℃/min, heating to 500 ℃ at a heating speed of 0.5 ℃/min, preserving heat for 10h, and naturally cooling to room temperature to obtain the modified hard carbon negative electrode material for the lithium ion battery; the carbon source is coal tar.
Example 3
A preparation method of a modified hard carbon negative electrode material for a lithium ion battery comprises the following steps:
1) firstly, adding phenol and strong base into a formaldehyde solution, and stirring and reacting for 8 hours at the temperature of 60 ℃ to obtain water-soluble phenolic resin; the mass ratio of the formaldehyde solution or the acetaldehyde solution is as follows: phenol: strong base 1: 2: 0.1; the concentration of the formaldehyde solution is 37 percent; the strong base is NaOH, and the purity is more than 99.9%.
2) Adding ammonium persulfate into the water-soluble phenolic resin prepared in the step 1), wherein the mass (g) of the ammonium persulfate is as follows: after the water-soluble phenolic resin is completely dissolved, adding vegetable oil with the same volume, uniformly mixing, pouring into a hydrothermal reaction kettle, placing into a microwave oven with the power of 1200w, heating for 400s, filtering after the reaction is finished, washing for 7 times by using water and ethanol, and drying at the temperature of 40 ℃ to obtain a solid hard carbon precursor; the purity of the ammonium persulfate is more than 99.9 percent; the vegetable oil is olive oil.
3) Under the protection of nitrogen or inert gas, heating the solid hard carbon precursor obtained in the step 2) to 400 ℃ at a heating rate of 3 ℃/min, preserving heat for 1h, then heating to 900 ℃ at a heating rate of 2 ℃/min, preserving heat for 10h, and naturally cooling to room temperature to obtain a hard carbon matrix;
4) carrying out ball milling or crushing on the hard carbon to obtain a hard carbon matrix with the granularity of 1-60 mu m;
5) adding a carbon source into a hard carbon matrix, uniformly mixing, heating to 400 ℃ at a rotation speed of 2500r/min for 100min under the protection of nitrogen or inert gas at a heating rate of 3 ℃/min, preserving heat for 1h, heating to 700 ℃ at a heating rate of 2 ℃/min, preserving heat for 9h, and naturally cooling to room temperature to obtain the modified hard carbon negative electrode material for the lithium ion battery; the carbon source is petroleum asphalt.
Example 4
A preparation method of a modified hard carbon negative electrode material for a lithium ion battery comprises the following steps:
1) firstly, adding phenol and strong base into a formaldehyde solution, and stirring and reacting for 7 hours at the temperature of 59 ℃ to obtain water-soluble phenolic resin; the mass ratio of the formaldehyde solution or the acetaldehyde solution is as follows: phenol: strong base 1: 2: 0.15; the concentration of the formaldehyde solution is 37 percent; the strong base is NaOH, and the purity is more than 99.9%.
2) Adding ammonium persulfate into the water-soluble phenolic resin prepared in the step 1), wherein the mass (g) of the ammonium persulfate is as follows: after the water-soluble phenolic resin is completely dissolved, adding vegetable oil with the same volume, uniformly mixing, pouring into a hydrothermal reaction kettle, placing into a microwave oven with the power of 1000w, heating for 190s, filtering after the reaction is finished, washing for 7 times by using water and ethanol, and drying at the temperature of 40 ℃ to obtain a solid hard carbon precursor; the purity of the ammonium persulfate is more than 99.9 percent; the vegetable oil is sesame oil.
3) Under the protection of nitrogen or inert gas, heating the solid hard carbon precursor obtained in the step 2) to 400 ℃ at a heating rate of 4 ℃/min, preserving heat for 1h, then heating to 700 ℃ at a heating rate of 3 ℃/min, preserving heat for 10h, and then naturally cooling to room temperature to obtain a hard carbon matrix;
4) carrying out ball milling or crushing on the hard carbon to obtain a hard carbon matrix with the granularity of 1-60 mu m;
5) adding a carbon source into a hard carbon matrix, uniformly mixing, heating to 400 ℃ at a rotation speed of 1500r/min for 62min under the protection of nitrogen or inert gas, keeping the temperature for 1h, heating to 800 ℃ at a heating speed of 2 ℃/min, keeping the temperature for 9h, and naturally cooling to room temperature to obtain the modified hard carbon negative electrode material for the lithium ion battery; the carbon source is petroleum asphalt.
Comparative example
Modified natural graphite material obtained by using pitch as a coating material.
Electrochemical performance tests were performed on the foregoing examples and comparative examples as follows:
in order to test the performance of the lithium ion battery negative electrode material of the invention, a half-cell test method is used for testing, the negative electrode material of the above embodiment and comparative example, SBR (solid content is 50%), CMC: Super-p is 95.5: 2: 1.5: 1 (weight ratio), a proper amount of deionized water is added to be blended into slurry, the slurry is coated on copper foil and dried in a vacuum drying oven for 12 hours to prepare a negative electrode sheet, the electrolyte is 1M LiPF6/EC + DEC + DMC is 1:1, a polypropylene microporous membrane is a diaphragm, a counter electrode is a lithium sheet, and the battery is assembled. Carrying out constant current charge and discharge experiment at LAND battery test system, charge and discharge voltage limits at 0.01 ~ 3.0V, carry out data's collection and control with computer control's charge and discharge cabinet, test temperature: 25 ℃ and 60 ℃. The data obtained are shown in table 1 below.
Table 1 shows the performance comparison of the negative electrode materials of the different examples and comparative examples.
As can be seen from table 1, the first charge-discharge efficiency of the modified hard carbon negative electrode material of the present invention is generally high, the lithium insertion and lithium removal performance of the modified hard carbon negative electrode material is good, and the high current charge-discharge performance and the cycle performance are excellent.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the technical scope of the present invention, so that any minor modifications, equivalent changes and modifications made to the above embodiment according to the technical spirit of the present invention are within the technical scope of the present invention.
Claims (5)
1. A preparation method of a modified hard carbon negative electrode material for a lithium ion battery is characterized by comprising the following steps: the method comprises the following steps:
1) Firstly, adding phenol and strong base into a formaldehyde solution or an acetaldehyde solution, and stirring and reacting for 5-12h at the temperature of 50-80 ℃ to obtain water-soluble phenolic resin; the mass ratio of the formaldehyde solution or the acetaldehyde solution is as follows: phenol: strong base 1: 2: 0.05 to 0.2;
2) Adding ammonium persulfate into the water-soluble phenolic resin prepared in the step 1), after completely dissolving, adding vegetable oil with the same volume, uniformly mixing, pouring into a hydrothermal reaction kettle, placing into a microwave oven with the power of 600-2000 w, heating for 10-600 s, filtering after the reaction is finished, washing for 3-10 times with water and ethanol, and drying at the temperature of 40 ℃ to obtain a solid hard carbon precursor; the mass of the ammonium persulfate in grams is as follows: the volume of the water-soluble phenolic resin is 1:10-50 in milliliters; the concentration of the formaldehyde solution is 37 percent, and the concentration of the acetaldehyde solution is 40 percent;
3) Under the protection of nitrogen or inert gas, heating the solid hard carbon precursor obtained in the step 2) to 400 ℃ at the heating rate of 1-5 ℃/min, preserving heat for 1h, then heating to 500-1200 ℃ at the heating rate of 0.5-3 ℃/min, preserving heat for 3-20h, and then naturally cooling to room temperature to obtain a hard carbon matrix;
4) Carrying out ball milling or crushing on the hard carbon to obtain a hard carbon matrix with the granularity of 1-60 mu m;
5) Adding a carbon source into a hard carbon matrix, uniformly mixing at the rotation speed of 500-3500r/min for 15-120min, heating to 400 ℃ at the heating speed of 2-5 ℃/min under the protection of nitrogen or inert gas, preserving heat for 1h, heating to 500-1200 ℃ at the heating speed of 0.5-3 ℃/min, preserving heat for 7-10h, and naturally cooling to room temperature to obtain the modified hard carbon cathode material for the lithium ion battery.
2. The preparation method of the modified hard carbon negative electrode material for the lithium ion battery according to claim 1, characterized in that: the strong base is at least one of NaOH and KOH, and the purity is more than 99.9%.
3. The preparation method of the modified hard carbon negative electrode material for the lithium ion battery according to claim 1, characterized in that: the purity of the ammonium persulfate is more than 99.9 percent.
4. The preparation method of the modified hard carbon negative electrode material for the lithium ion battery according to claim 1, characterized in that: the vegetable oil is at least one of sesame oil, rapeseed oil or olive oil.
5. The preparation method of the modified hard carbon negative electrode material for the lithium ion battery according to claim 1, characterized in that: the carbon source in the step 5) is at least one of petroleum asphalt, coal asphalt and coal tar.
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| CN106450313B (en) * | 2016-11-15 | 2019-10-08 | 宁夏博尔特科技有限公司 | Porous hard carbon lithium ion cell negative electrode material and preparation method thereof and lithium ion battery |
| CN106450320B (en) * | 2016-12-12 | 2019-09-24 | 华中科技大学 | A kind of method and its application preparing hard carbon |
| CN106744798B (en) * | 2016-12-12 | 2019-04-09 | 华中科技大学 | A kind of method and its application preparing hard carbon using carbon containing biological mass shell |
| CN109921020A (en) * | 2017-12-13 | 2019-06-21 | 宁波杉杉新材料科技有限公司 | A kind of preparation method of high-capacity lithium ion cell hard charcoal negative electrode material |
| CN109786694B (en) * | 2018-12-28 | 2022-04-22 | 云南中晟新材料有限责任公司 | Preparation method of hard carbon negative electrode material of lithium battery |
| KR20220150952A (en) * | 2020-04-10 | 2022-11-11 | 가부시끼가이샤 구레하 | Method for manufacturing carbonaceous material for negative electrode of nonaqueous electrolyte secondary battery, method for manufacturing electrode for nonaqueous electrolyte secondary battery, and method for manufacturing nonaqueous electrolyte secondary battery |
| CN114373924A (en) * | 2020-10-14 | 2022-04-19 | 天津工业大学 | Green phenolic resin-based hard carbon negative electrode material for lithium/sodium ion battery and preparation method thereof |
| CN115449041A (en) * | 2021-06-09 | 2022-12-09 | 济南精智方正新材料有限公司 | Preparation method of micro-spherical phenolic resin |
| CN113437295B (en) * | 2021-06-18 | 2022-10-18 | 青海凯金新能源材料有限公司 | Hard carbon negative electrode material and preparation method thereof |
| CN115849331A (en) * | 2021-09-24 | 2023-03-28 | 胡启章 | Hard carbon microbead, its preparation method and energy storage device containing same |
| CN114975869B (en) * | 2022-06-06 | 2024-03-08 | 榆林学院 | Button sodium ion battery and preparation method thereof |
| CN115036479B (en) * | 2022-06-13 | 2023-04-25 | 成都佰思格科技有限公司 | Composite negative electrode material, preparation method thereof and sodium ion battery |
| CN117466278A (en) * | 2023-11-01 | 2024-01-30 | 东北大学 | Method for ball milling modification of hard carbon material and application of ball milling modification of hard carbon material in negative electrode of sodium ion battery |
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