CN107706417B - Preparation method of spherical carbon negative electrode material of lithium ion battery - Google Patents
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Abstract
The invention relates to a preparation method of a spherical carbon negative electrode material of a lithium ion battery. The method comprises the steps of taking starch as a raw material, uniformly mixing the starch with iron powder according to a certain proportion, carrying out stabilization treatment in an air atmosphere at the temperature of 200-250 ℃, then carrying out high-temperature carbonization in an inert atmosphere, and obtaining the spherical carbon negative electrode material through acid washing, water washing, suction filtration and drying. The iron powder is added to separate starch granules from each other, so that the phenomenon that the starch granules are heated unevenly is avoided, the stabilization time is greatly shortened, and the prepared carbon microspheres keep the original shape of the starch granules and have the grain diameter of 2-40 mu m. The method has simple process and low requirement on equipment, and the obtained carbon microspheres have excellent appearance and show excellent electrochemical performance when being used as the cathode material of the lithium ion battery.
Description
Technical Field
The invention relates to a preparation method of spherical carbon and application of the spherical carbon in a lithium ion battery, and belongs to the technical field of lithium ion battery cathode materials.
Background
The electronic product plays an increasingly important role in our daily life, the market competition of the battery is fierce, and the lithium ion battery has the advantages of large energy density, high average output voltage, good cycle stability, long service life, small volume, light weight, no memory effect, safety, reliability and the like, and is widely applied to the fields of consumer electronics, electric automobiles, energy storage and the like.
The improvement of the capacity of the lithium ion battery cathode material is one of the keys of the improvement of the energy density of the lithium ion battery cathode material. The carbon material is an ideal choice for the cathode material of the lithium ion battery, and is mainly applied most widely by graphite materials at present. With the expansion of the application field of lithium ion batteries, the performance requirements of the lithium ion batteries are continuously improved, and the limitations of the graphite cathode materials in the aspects of specific energy, cycle performance, safety and the like are more and more prominent. The carbon microspheres have good thermal stability, heat conductivity, high stacking density and low surface area to volume ratio, and can reduce irreversible capacity loss caused by side reactions such as SEI (solid electrolyte interphase) films, thereby being beneficial to improving the electrochemical performance of the lithium ion battery and being a research hotspot.
In the document "Non-catalytic CVD preparation of Carbon spheres with a specific size (Carbon,2004,42(4), 761-766)", the authors prepared spherical Carbon materials from toluene using a self-made two-furnace chemical vapor deposition apparatus without the addition of a catalyst. In The document "The production of Carbon materials by hydrothermal digestion of cellulose Carbon,2009.47(9): 2281-2289", Carbon microspheres are prepared by hydrothermal method and KOH activation using cellulose, eucalyptus wood chips, etc. as Carbon sources. Liyongfeng, etc. uses coal as raw material, changes the condition of plasma to prepare carbon microsphere, the preparation process is completed on a DC arc plasma evaporation experimental device (a novel coal-based spherical carbon and the forming mechanism thereof, university of general organization, 2002,42(6): 663-668). In the document "Monodisspersed hard carbon spheres with inorganic nanoparticles", sucrose is used as a carbon source, dehydration is carried out at 190 ℃ under a closed condition, and high-temperature carbonization is carried out under an argon atmosphere to prepare the product with the specific surface area of 400m2Monodisperse carbon microspheres per gram. In summary, many preparation methods of carbon microspheres have high requirements on experimental conditions and equipment, the commercialization process of carbon microsphere negative electrode materials is limited to a great extent, and most of precursors for preparing carbon microspheres are non-renewable or environmentally unfriendly precursors. Therefore, the preparation process is simplified, and the yield is improved by adopting the environment-friendly precursor, so that the research direction of the carbon microspheres is formed. The starch has rich sources and low cost, and the carbon microsphere material which keeps the original spherical shape of the starch granules can be prepared by the early oxidation treatment, so that the difficulty of the balling process is reduced, the preparation cost of the lithium ion battery cathode material is reduced, the raw materials are green, environment-friendly and renewable, and the problem of shortage of fossil resources is alleviated.
The patent CN103647082A prepares the hard carbon microsphere negative electrode material through low-temperature stabilization and high-temperature carbonization under the condition of reduced pressure, the method can avoid the caking phenomenon of the carbonized carbon microsphere, reduce the irreversible capacity of the hard carbon microsphere and improve the cycling stability of the material. In order to eliminate the foaming and caking phenomena of the carbon microspheres, the method needs long-time (8-100h) low-temperature stabilization treatment, so that the preparation time of the carbon microspheres is too long, and the preparation efficiency is reduced. Patent CN102364727A compounds starch-based hard carbon microspheres and expanded graphite to form an artificial solid space conductive network structure, thereby improving the voltage hysteresis of hard carbon materials and improving the first efficiency of the materials. The process for compounding the carbon microspheres and the expanded graphite in the method is complicated, and the preparation cost of the material is increased.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a method for preparing spherical carbon for a lithium ion battery cathode by taking starch as a precursor and adding iron powder to shorten the stabilization time.
The technical scheme adopted by the invention is as follows: a preparation method of spherical carbon comprises the following specific steps:
1. uniformly mixing raw material starch and iron powder according to a certain proportion, and performing heating stabilization pretreatment within the temperature range of 200-250 ℃;
2. placing the stabilized sample in the step 1 in a high-temperature tube furnace, carrying out high-temperature carbonization for 0.5-3h in the temperature range of 600-1200 ℃ under inert atmosphere, and cooling to obtain a carbonized product;
3. and (3) pickling the carbonized product in the step (2), washing with deionized water, performing suction filtration, and drying to obtain the spherical carbon negative electrode material of the lithium ion battery.
Preferably, the starch raw material in the step 1 is at least one of potato starch, corn starch, wheat starch, tapioca starch, rice starch, sweet potato starch and mung bean starch.
Preferably, the iron powder in the step 1 is high-purity iron powder with a particle size of 300-1000 meshes.
Preferably, the mixing ratio of the starch to the iron powder in the step 1 is 1: 1-100: 1.
preferably, the stabilizing treatment time in the step 1 is 1-12 h.
Preferably, the inert atmosphere in step 2 is high purity nitrogen.
Preferably, the carbonization temperature in step 2 is 700-.
Preferably, the carbonization time in the step 2 is 1-2 h.
Preferably, the acid used in step 3 is 1% dilute hydrochloric acid.
The invention has the characteristics of rich raw material sources, low cost, simple preparation process, no pollution and the like. Carry out stabilization through adding the iron powder in starch, separate starch granule each other, under same stabilization temperature, can avoid the melt between the starch granule, starch granule because of piling up inhomogeneous phenomenon of being heated each other, shortened the earlier stage stabilization time of starch greatly, resources are saved for preparation efficiency can promote.
The starch particles are separated from each other by adding the iron powder and are subjected to stabilization or carbonization treatment, so that the starch particles are uniformly heated, and the consistency of the prepared sample is improved. The operation process is simple, the requirement on equipment is low, and large-scale preparation and production are easy to realize. The starch-based carbon microsphere prepared by the invention has good spherical shape, and shows excellent cycle stability and rate capability when being used as a lithium ion battery cathode material.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of a raw potato starch used in the present invention.
Fig. 2 is a scanning electron microscope image of the starch-based carbon microsphere negative electrode material prepared in example 1 of the present invention.
FIG. 3 is a scanning electron microscope image of the starch-based carbon microsphere negative electrode material prepared in comparative example 1 of the present invention.
FIG. 4 is a cycle performance curve of the carbon microsphere negative electrode material prepared in example 1 at a current density of 50 mA/g.
FIG. 5 is a rate performance curve of the carbon microsphere negative electrode material prepared in example 1 at a current density of 0.05-2A/g.
Detailed Description
The present invention is further illustrated by the following examples, which are not to be construed as limiting the invention thereto.
Example 1
Fully stirring and mixing 10g of potato starch and 10g of iron powder, putting the mixture into a muffle furnace, heating to 230 ℃ at a heating rate of 5 ℃/min for 8 hours in an air atmosphere, carrying out stabilization treatment, then putting a stabilized sample into a carbonization furnace, heating to 700 ℃ at a heating rate of 1.5 ℃/min for 1 hour in a nitrogen atmosphere. And (3) placing the carbide in a beaker, adding 1% diluted hydrochloric acid for treatment, then washing with deionized water for a plurality of times, carrying out suction filtration and drying to obtain the potato starch-based carbon microspheres with the particle size range of 5.5-32.6 microns.
The obtained carbon microspheres are used as a lithium ion battery cathode material to assemble a battery, and the cycle performance and the rate performance of the battery are tested. The test conditions were: at 25 deg.C, the current density is 0.05-2A/g, and the voltage range is 0.01-3V.
As shown in the attached figure 5, when the obtained carbon microspheres are used as a lithium ion battery negative electrode material, the reversible specific capacity is 323.2mAh/g under the current density of 50 mA/g. Under the current density of 2A/g, the reversible specific capacity is 82.7 mAh/g. The cycle performance is excellent, and when the current density returns to 50mA/g, the reversible specific capacity reaches 336.3 mAh/g.
Example 2
Fully stirring and mixing 10g of potato starch and 0.1g of iron powder, putting the mixture into a muffle furnace, heating to 230 ℃ at a heating rate of 5 ℃/min under the air atmosphere, preserving the temperature for 8h, carrying out stabilization treatment, then putting a stabilized sample into a carbonization furnace, heating to 700 ℃ at a heating rate of 1.5 ℃/min under the nitrogen atmosphere, and keeping the temperature for 1 h. And (3) placing the carbide in a beaker, adding 1% diluted hydrochloric acid for treatment, then washing with deionized water for a plurality of times, carrying out suction filtration and drying to obtain the potato starch-based carbon microspheres with the particle size range of 6.0-30.66 mu m. The obtained carbon material is assembled into a battery and subjected to electrochemical performance test, the current density is 50mAh/g, the first discharge specific capacity is 645.6mAh/g, the reversible specific capacity is 350.5mAh/g, and the capacity retention rate after 50 times of circulation is 70%.
Example 3
Fully stirring and mixing 10g of potato starch and 1g of iron powder, putting the mixture into a muffle furnace, heating to 230 ℃ at a heating rate of 5 ℃/min for 8 hours in an air atmosphere, carrying out stabilization treatment, then putting a stabilized sample into a carbonization furnace, heating to 700 ℃ at a heating rate of 1.5 ℃/min for 1 hour in a nitrogen atmosphere. And (3) placing the carbide in a beaker, adding 1% dilute hydrochloric acid for treatment, then washing the carbide for a plurality of times by using deionized water, carrying out suction filtration and drying to obtain the potato starch-based carbon microspheres. The particle size range is 3.9-28.13 μm.
Example 4
Fully stirring and mixing 10g of potato starch and 1g of iron powder, putting the mixture into a muffle furnace, heating to 230 ℃ at a heating rate of 5 ℃/min for heat preservation for 12h under an air atmosphere, carrying out stabilization treatment, then putting a stabilized sample into a carbonization furnace, heating to 700 ℃ at a heating rate of 1.5 ℃/min for heat preservation for 1h under a nitrogen atmosphere. And (3) placing the carbide in a beaker, adding 1% dilute hydrochloric acid for treatment, then washing the carbide for a plurality of times by using deionized water, carrying out suction filtration and drying to obtain the potato starch-based carbon microspheres.
Example 5
Fully stirring and mixing 10g of potato starch and 1g of iron powder, putting the mixture into a muffle furnace, heating to 230 ℃ at a heating rate of 5 ℃/min for heat preservation for 2h under an air atmosphere, carrying out stabilization treatment, then putting a stabilized sample into a carbonization furnace, heating to 700 ℃ at a heating rate of 1.5 ℃/min for heat preservation for 1h under a nitrogen atmosphere. And (3) placing the carbide in a beaker, adding 1% dilute hydrochloric acid for treatment, then washing the carbide for a plurality of times by using deionized water, carrying out suction filtration and drying to obtain the potato starch-based carbon microspheres.
Example 6
Fully stirring and mixing 10g of potato starch and 1g of iron powder, putting the mixture into a muffle furnace, heating to 230 ℃ at a heating rate of 5 ℃/min for 8 hours in an air atmosphere, carrying out stabilization treatment, then putting a stabilized sample into a carbonization furnace, heating to 1000 ℃ at a heating rate of 1.5 ℃/min for 1 hour in a nitrogen atmosphere. And (3) placing the carbide in a beaker, adding 1% dilute hydrochloric acid for treatment, then washing the carbide for a plurality of times by using deionized water, carrying out suction filtration and drying to obtain the potato starch-based carbon microspheres. The particle size range is 6-32 μm.
Example 7
Fully stirring and mixing 10g of corn starch and 10g of iron powder, putting the mixture into a muffle furnace, heating to 230 ℃ at a heating rate of 5 ℃/min for heat preservation for 8 hours in an air atmosphere, carrying out stabilization treatment, then putting a stabilized sample into a carbonization furnace, heating to 700 ℃ at a heating rate of 1.5 ℃/min for heat preservation for 1 hour in a nitrogen atmosphere. And (3) placing the carbide in a beaker, adding 1% diluted hydrochloric acid for treatment, then washing the carbide for a plurality of times by using deionized water, carrying out suction filtration and drying to obtain the corn starch-based carbon material.
Example 8
Fully stirring and mixing 10g of wheat starch and 10g of iron powder, putting the mixture into a muffle furnace, heating to 230 ℃ at a heating rate of 5 ℃/min for heat preservation for 8 hours in an air atmosphere, carrying out stabilization treatment, then putting a stabilized sample into a carbonization furnace, heating to 700 ℃ at a heating rate of 1.5 ℃/min for heat preservation for 1 hour in a nitrogen atmosphere. And (3) placing the carbide in a beaker, adding 1% dilute hydrochloric acid for treatment, then washing the carbide for a plurality of times by using deionized water, carrying out suction filtration and drying to obtain the wheat starch-based carbon material.
Comparative example 1
Putting 10g of potato starch into a muffle furnace, heating to 230 ℃ at a heating rate of 5 ℃/min for 8h under the air atmosphere, carrying out stabilization treatment, then putting a stabilized sample into a carbonization furnace, heating to 700 ℃ at a heating rate of 1.5 ℃/min under the nitrogen atmosphere, keeping for 1h, and cooling to obtain the potato starch-based carbon material. In this example, compared with example 1, the direct stabilization of potato starch resulted in the formation of fusion and adhesion of starch granules during post-carbonization, which failed to maintain the spherical shape of the potato starch granules.
Although some embodiments of the present invention have been described in detail, the present invention is not limited to the above-described embodiments, and those skilled in the art can make equivalent modifications or substitutions without departing from the spirit of the present invention, and such equivalent modifications or substitutions are included in the scope of the present invention defined by the claims.
Claims (4)
1. A preparation method of a spherical carbon negative electrode material of a lithium ion battery is provided, the particle diameter of the spherical carbon negative electrode material is 2-40 μm, and the preparation method is characterized by comprising the following steps:
(1) the starch raw material is at least one of potato starch, corn starch, wheat starch, tapioca starch, rice starch and mung bean starch, the starch raw material and iron powder are fully and uniformly mixed according to a certain proportion, and the mixture is subjected to heating stabilization pretreatment for 1-12h within the temperature range of 200-;
(2) placing the stabilized sample in the step (1) in an inert atmosphere, carbonizing at the temperature of 600-1200 ℃ for 0.5-3h, and cooling to obtain a carbonized product;
(3) and (3) pickling the carbide obtained in the step (2), washing with deionized water, performing suction filtration, and drying to obtain the spherical carbon negative electrode material of the lithium ion battery.
2. The preparation method of the spherical carbon negative electrode material of the lithium ion battery according to claim 1, characterized by comprising the following steps: the particle size of the iron powder is 300-1000 meshes.
3. The preparation method of the spherical carbon negative electrode material of the lithium ion battery according to claim 1, characterized by comprising the following steps: the mixing ratio of the starch and the iron powder in the step (1) is 1: 1-500: 1.
4. the preparation method of the spherical carbon negative electrode material of the lithium ion battery according to claim 1, characterized by comprising the following steps:
the acid in the step (3) is 1% dilute hydrochloric acid.
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| CN108461708A (en) * | 2018-04-08 | 2018-08-28 | 毛强平 | A kind of lithium ion battery negative material, preparation method and lithium ion battery |
| CN109686975A (en) * | 2018-12-05 | 2019-04-26 | 桑德集团有限公司 | A kind of hard charcoal negative electrode material and preparation method thereof |
| CN113224300B (en) * | 2021-04-15 | 2022-07-29 | 淄博火炬能源有限责任公司 | Preparation method of lead powder for negative electrode of lead-carbon battery |
| CN114988391B (en) * | 2022-06-29 | 2023-04-11 | 宜昌邦普循环科技有限公司 | Preparation method and application of hard carbon negative electrode material |
| DE112022000467T5 (en) * | 2022-06-29 | 2024-02-15 | Guangdong Brunp Recycling Technology Co., Ltd. | METHOD FOR PRODUCING HARD CARBON ANODE MATERIAL AND USE THEREOF |
| CN115602838A (en) * | 2022-10-21 | 2023-01-13 | 南自通华（南京）智能电气有限公司（Cn） | Spherical carbon negative electrode material of lithium ion battery and preparation method thereof |
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