CN109148865B - Preparation method of hard carbon composite carbon microsphere negative electrode material of lithium or sodium ion battery - Google Patents
Preparation method of hard carbon composite carbon microsphere negative electrode material of lithium or sodium ion battery Download PDFInfo
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- CN109148865B CN109148865B CN201811039705.9A CN201811039705A CN109148865B CN 109148865 B CN109148865 B CN 109148865B CN 201811039705 A CN201811039705 A CN 201811039705A CN 109148865 B CN109148865 B CN 109148865B
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- H—ELECTRICITY
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- 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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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- 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
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- H—ELECTRICITY
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- 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
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- 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
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- H—ELECTRICITY
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- 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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- 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 composite carbon microspheres, which comprises the following steps: (1) placing graphene oxide and a high polymer material in water or an organic solvent, and performing ultrasonic treatment to obtain a compound spray solution; (2) carrying out spray drying on the compound spray liquid obtained in the step (1) to obtain a compound carbon microsphere precursor; (3) and (3) carrying out high-temperature carbonization on the composite carbon microsphere precursor obtained in the step (2) under the protection of inert gas to obtain the composite carbon microsphere. The preparation method provided by the invention can obtain the graphene-coated hard carbon composite carbon microspheres with good appearance and excellent performance without a stabilization process, and the graphene-coated hard carbon composite carbon microspheres have good stability and good rate charge and discharge performance when being applied to batteries.
Description
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to a preparation method of a composite carbon microsphere material with hard carbon surface coated with graphene oxide for a lithium or sodium ion battery cathode and application of the obtained composite carbon microsphere in battery materials.
Background
The lithium ion battery has the characteristics of high specific energy, high working voltage, long cycle life, no memory effect and the like, and is widely used in the fields of electric automobiles, mobile communication equipment power supplies and the like. The sodium ion battery has similar characteristics with the lithium ion battery, is rich in sodium resource, has lower price compared with lithium, and receives more and more attention in the field of large-scale energy storage. The lithium and sodium ion battery mainly comprises a positive electrode, a negative electrode, a diaphragm, electrolyte and the like, wherein the positive electrode and the negative electrode are main factors determining the performance of the battery. In terms of negative electrode materials, the lithium ion negative electrode which is commercialized at present is mainly graphite, but the development of the lithium ion negative electrode is limited due to the lower theoretical specific capacity of the lithium ion negative electrode, and the lithium ion negative electrode cannot be applied to a sodium ion battery due to the smaller interlayer spacing of the lithium ion negative electrode. Therefore, designing and preparing a high-performance negative electrode material is crucial to the development of lithium and sodium ion batteries.
Attention is now being directed to other carbon materials, such as soft carbon, hard carbon. Among them, hard carbon has attracted much interest because of its higher capacity, lower cost and excellent cycle performance. The hard carbon refers to non-graphitizable carbon, is pyrolytic carbon of high molecular polymers, and can be obtained by carbonizing cross-linked resin with a special structure at about 1000 ℃. Hard carbon is difficult to graphitize at high temperature above 2500 ℃; the reversible specific capacity of the lithium ion battery is high, and is generally 500-700 mAh/g. In addition, since the interlayer spacing of hard carbon is larger than that of graphite, sodium ions can be intercalated and deintercalated, and thus it is considered as a sodium ion negative electrode material most likely to be commercialized.
High molecular materials such as sucrose, starch and the like can be used as precursors to prepare hard carbon for lithium ion and sodium ion battery cathode materials through pyrolysis and carbonization processes. However, high polymer materials such as sucrose and starch are crystalline high polymer materials and contain crystal water, and the structure can be melted and deformed through reaction processes such as dehydration, cracking and polycondensation in the pyrolysis and carbonization processes, so that the obtained hard carbon spheres can be adhered into blocks, and the performance of the obtained hard carbon can be reduced when the obtained hard carbon is used for a lithium/sodium ion negative electrode material. In order to prevent the problems of rapid dehydration and foaming, the existing preparation method can carry out low-temperature stabilization for a long time (such as more than 24 hours) before carbonization, thereby prolonging the preparation time and wasting a large amount of energy.
The present invention has been made to solve the above problems.
Disclosure of Invention
Aiming at the defect that the traditional process for preparing hard carbon by organic polymer materials such as sucrose and starch needs long-time stabilization treatment, the invention discloses a preparation method of a composite carbon microsphere by coating graphene oxide serving as a negative electrode material of a lithium/sodium ion battery on the surface of the hard carbon. The composite carbon microsphere is formed by coating graphene oxide on the surface of hard carbon, is irregular monodisperse particles, has good structural stability and dispersibility, is not adhered to each other, and can keep a high dispersion state. The invention solves the defects that the polymer material is easy to soften, generates foaming and adhesion agglomeration, and further causes poor battery performance and the like due to direct high-temperature carbonization.
The specific technical scheme of the invention is as follows:
the invention discloses a preparation method of composite carbon microspheres in a first aspect, which comprises the following steps:
(1) placing graphene oxide and a high polymer material in water or an organic solvent, and performing ultrasonic treatment to obtain a compound spray solution;
(2) carrying out spray drying on the spray liquid obtained in the step (1) to obtain a composite carbon microsphere precursor;
(3) and (3) carrying out high-temperature carbonization on the composite carbon microsphere precursor obtained in the step (2) under the protection of inert gas to obtain the composite carbon microsphere.
Preferably, the polymer material in step (1) is a biopolymer material or a synthetic polymer material; such as starch, sucrose, lignin, cellulose, hemicellulose, pitch, phenolic resin, etc.; the mass ratio of the graphene oxide to the high polymer material is 1 (4-20).
Preferably, the organic solvent in step (1) is one or more of ethanol, acetone, N-2-methylformamide, benzene and derivatives thereof.
Preferably, the power of the ultrasonic treatment in the step (1) is 20kHz, and the time is 30-60 min.
Preferably, the solid content of the compound spray liquid in the step (1) is 3-10 wt%.
Preferably, the temperature of the spray drying in the step (2) is 100-.
Preferably, the inert gas in step (3) is nitrogen or argon.
Preferably, the high-temperature carbonization temperature in the step (3) is 700-1600 ℃, and the time is 1-3 h.
Preferably, the obtained composite carbon microsphere is formed by coating graphene oxide on the surface of hard carbon, and is irregular monodisperse spherical particles.
The invention also discloses application of the composite carbon microsphere prepared by the preparation method to a battery cathode material.
The invention has the beneficial effects that:
1. according to the invention, the high polymer material and the graphene oxide are compounded in a spray self-assembly manner, the graphene-coated hard carbon composite carbon microsphere with good appearance and excellent performance can be obtained without a stabilization process, and the composite carbon microsphere is applied to the negative electrode of a lithium or sodium ion battery, so that the specific capacity and the rate capability of the battery are improved; and the stability of the battery is good.
2. The preparation method does not need a low-temperature stabilization process before the composite carbon microsphere precursor is carbonized at high temperature, so that the preparation time is greatly shortened, and the energy is saved.
3. The composite carbon microsphere prepared by the invention has the advantages of no bonding among particles, good dispersibility, and contribution to coating and film forming in the later electrode preparation process and improvement of the electrode surface flatness.
4. The preparation method has the advantages of simple equipment, easily controlled operation process, high preparation efficiency, stable product performance and high cost performance.
Drawings
Fig. 1 is an SEM photograph of the composite carbon microsphere prepared in example 1.
Fig. 2 is a first charge-discharge diagram of the composite carbon microsphere prepared in example 1 as a negative electrode material of a lithium ion battery at 0.1C.
Fig. 3 is an SEM photograph of a sample of starch without added graphene oxide in example 1 after carbonization under the same conditions.
Fig. 4 is a first charge-discharge diagram of a lithium ion battery assembled from samples, which are carbonized under the same conditions, of starch without graphene oxide, corresponding to example 1, at 1C.
Fig. 5 is an SEM photograph of the composite carbon microsphere prepared in example 2.
Fig. 6 is a first charge-discharge diagram of the composite carbon microsphere prepared in example 2 as a negative electrode material of a sodium-ion battery at 0.1C.
Fig. 7 is an SEM photograph of a sample of starch without added graphene oxide of example 2 after carbonization under the same conditions.
Fig. 8 is a first charge-discharge diagram of a sodium ion battery assembled by samples of starch without graphene oxide under the same conditions, which corresponds to example 2, and which is carbonized under the same conditions, at 0.1C.
Fig. 9 is an SEM photograph of the composite carbon microsphere prepared in example 3.
Fig. 10 is a first charge-discharge diagram of the composite carbon microsphere prepared in example 3 as a negative electrode material of a sodium-ion battery at 0.1C.
Fig. 11 is an SEM photograph of a sample of the pitch without graphene oxide added of example 3 after carbonization under the same conditions.
Fig. 12 is a first charge-discharge diagram of a sodium ion battery assembled by samples of pitch without graphene oxide under the same conditions, which corresponds to example 3, after carbonization at 0.1C.
Detailed Description
The present invention will be further described below by way of specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations based on the knowledge and conventional practices of the ordinary skill in the art are intended to be included within the scope of the present invention without departing from the spirit thereof.
Example 1
Adding 0.5g of graphene oxide and 9.5g of water-soluble starch into 323ml of deionized water, and performing ultrasonic treatment at 20kHz for 45min to obtain a spray liquid with the solid content of 3 wt%; and (3) carrying out spray self-assembly on the obtained spray liquid by using a spray dryer to obtain a starch/graphene oxide composite carbon microsphere precursor, wherein the parameters in the spray process are as follows: the temperature of an air inlet is 120 ℃, the frequency of a fan is 60Hz, and the feeding speed is 500 ml/h; and placing the obtained starch/graphene oxide composite carbon microsphere precursor in a corundum crucible, placing the corundum crucible in a tubular furnace, and preserving heat for 2 hours at the high temperature of 700 ℃ under the protection of nitrogen so as to pyrolyze and carbonize starch, thereby obtaining the composite carbon microsphere. The scanning electron micrograph thereof is shown in FIG. 1. As can be seen from FIG. 1, the prepared sample is monodisperse particles with graphene oxide coated on the surface of the microsphere, no adhesion exists between the particles, and the dispersibility is good. Fig. 3 is an SEM photograph of a sample after carbonization of starch without added graphene oxide under the same conditions, and it can be seen that the sample has been agglomerated, the adhesion is severe, and it is not a monodisperse particle.
The composite carbon microsphere obtained in example 1 is used as a negative electrode material in a lithium ion battery, and the constant current charge and discharge performance of the lithium ion battery at 0.1 ℃ is tested, and the first charge and discharge curve chart is shown in fig. 2. As can be seen from FIG. 2, the specific capacity of the composite carbon microsphere prepared in the embodiment 1 for the lithium ion battery is higher than 600mAh/g, and the performance is excellent. Fig. 4 is a first charge-discharge curve diagram of a lithium ion battery assembled by samples carbonized by starch without graphene oxide under the same conditions corresponding to the embodiment 1, and it can be seen from fig. 4 that the lithium ion battery assembled by the samples carbonized by starch without graphene oxide under the same conditions has a specific capacity of less than 500 mAh/g.
Example 2
Adding 1g of graphene oxide and 9g of water-soluble starch into 323ml of deionized water, and carrying out ultrasonic treatment for 60min at 20kHz by using a powerful ultrasonic machine to obtain a spray liquid with the solid content of 3 wt%; and (3) carrying out spray self-assembly on the obtained spray liquid by using a spray dryer to obtain a starch/graphene oxide composite carbon microsphere precursor, wherein the parameters in the spray process are as follows: the temperature of an air inlet is 120 ℃, the frequency of a fan is 60Hz, and the feeding speed is 500 ml/h; and placing the obtained starch/graphene oxide composite carbon microsphere precursor in a corundum crucible, placing the corundum crucible in a tubular furnace, and preserving heat for 3 hours at the high temperature of 900 ℃ under the protection of nitrogen so as to pyrolyze and carbonize starch, thereby obtaining the composite carbon microsphere. The scanning electron micrograph of the composite carbon microsphere is shown in fig. 5, and it can be seen from fig. 5 that the graphene oxide sample prepared in example 2 is coated on the surface of the microsphere, and the composite carbon microsphere is a monodisperse particle after carbonization, so that the particles are free from adhesion and have good dispersibility. Fig. 7 is an SEM photograph of a sample after carbonization of starch without added graphene oxide under the same conditions, and it can be seen that the sample has been agglomerated, the adhesion is severe, and it is not a monodisperse particle.
The composite carbon microsphere obtained in example 2 was used as a negative electrode active material and assembled into a sodium ion battery, and the constant current charge and discharge performance at 0.1C was tested, and the first charge and discharge curve thereof is shown in fig. 6. As can be seen from FIG. 6, the specific capacity of the composite carbon microsphere prepared in example 2 for the sodium-ion battery is higher than 300 mAh/g. Fig. 8 is a first charge-discharge curve diagram of a sodium ion battery assembled by samples of starch without graphene oxide under the same conditions, corresponding to example 2; as can be seen from FIG. 8, the lithium ion battery assembled by the sample carbonized under the same conditions without the graphene oxide has a specific capacity of less than 200 mAh/g.
Example 3
Adding 1g of graphene oxide and 9g of asphalt into 323ml of N, N-2-methylformamide, and carrying out ultrasonic treatment for 60min at 20kHz by using a powerful ultrasonic machine to obtain spray liquid with the solid content of 3 wt%; and (3) carrying out spray self-assembly on the obtained spray solution by using a spray dryer to obtain an asphalt/graphene oxide composite carbon microsphere precursor, wherein the parameters in the spray process are as follows: the temperature of an air inlet is 180 ℃, the frequency of a fan is 60Hz, and the feeding speed is 500 ml/h; the obtained pitch/graphene oxide composite carbon microsphere precursor is placed in a corundum crucible, and then is placed in a tubular furnace to be insulated for 3 hours at the high temperature of 900 ℃ under the protection of nitrogen, so that pitch is pyrolyzed and carbonized, and the composite carbon microsphere is obtained, wherein a scanning electron micrograph of the composite carbon microsphere is shown in figure 9, and it can be seen from figure 9 that the sample graphene oxide prepared in example 3 is coated on the surface of the microsphere, the composite carbon microsphere is monodisperse particles after carbonization, no adhesion exists among the particles, and the dispersibility is good. Fig. 11 is an SEM photograph of a sample after the pitch without graphene oxide is carbonized under the same conditions, and it can be seen that the sample has been agglomerated and the particles are seriously adhered.
The composite carbon microsphere obtained in example 3 was used as a negative electrode in a sodium ion battery, and the constant current charge and discharge performance at 0.1C was tested, and the first charge and discharge curve graph is shown in fig. 10. As can be seen from FIG. 10, the specific capacity of the composite carbon microsphere prepared in example 3 for the sodium ion battery is higher than 250mAh/g, and the composite carbon microsphere has good electrochemical performance. Fig. 12 is a first charge-discharge curve diagram of a sodium ion battery assembled by samples which are carbonized under the same conditions and without addition of graphene oxide corresponding to example 3; as can be seen from FIG. 12, the lithium ion battery assembled by the sample carbonized under the same conditions without the graphene oxide has a specific capacity of less than 200 mAh/g.
Claims (8)
1. The preparation method of the composite carbon microsphere is characterized by comprising the following steps:
(1) placing a raw material consisting of graphene oxide and a high polymer material in water or an organic solvent, and performing ultrasonic treatment to obtain a compound spray solution;
(2) carrying out spray drying on the compound spray liquid obtained in the step (1) to obtain a compound carbon microsphere precursor;
(3) carrying out high-temperature carbonization on the composite carbon microsphere precursor obtained in the step (2) under the protection of inert gas to obtain the composite carbon microsphere;
the obtained composite carbon microsphere is formed by coating graphene oxide on the surface of carbon.
2. The method according to claim 1, wherein the polymer material of step (1) is a biopolymer material or a synthetic polymer material; the mass ratio of the graphene oxide to the high polymer material is 1 (4-20).
3. The preparation method according to claim 1, wherein the organic solvent in step (1) is one or more of ethanol, acetone, N-2-methylformamide and benzene.
4. The preparation method according to claim 1, wherein the ultrasonic treatment in the step (1) has a power of 20kHz and a time of 30-60 min.
5. The method according to claim 1, wherein the solid content of the spray liquid of the compound of step (1) is 3 to 10 wt%.
6. The method as claimed in claim 1, wherein the temperature of the spray drying in step (2) is 100-180 ℃, the feeding rate is 200-2000ml/h, and the wind speed is 50-70 Hz.
7. The method according to claim 1, wherein the inert gas in the step (3) is nitrogen or argon.
8. The method as claimed in claim 1, wherein the high temperature carbonization temperature in step (3) is 700-1600 ℃ for 1-3 h.
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| CN114156456B (en) * | 2021-12-08 | 2023-04-14 | 西北工业大学 | High-capacity rapid charge-discharge graphene @ hard carbon composite material, preparation method thereof and application of composite material in sodium ion battery |
| CN114597404A (en) * | 2022-03-02 | 2022-06-07 | 江西正拓新能源科技股份有限公司 | Lithium ion battery long-cycle hard carbon negative electrode material and preparation method thereof |
| CN114873579A (en) * | 2022-05-10 | 2022-08-09 | 山东能源集团有限公司 | Composite carbon microsphere, preparation method and application thereof |
| CN115020668A (en) * | 2022-06-27 | 2022-09-06 | 广州鹏辉能源科技股份有限公司 | Carbon-based negative electrode for sodium/potassium ion battery and preparation method thereof |
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| CN102544459A (en) * | 2012-01-09 | 2012-07-04 | 上海交通大学 | Method for preparing graphene-coated carbon microsphere material by coating graphene oxide on carbon microsphere |
| US8580432B2 (en) * | 2008-12-04 | 2013-11-12 | Nanotek Instruments, Inc. | Nano graphene reinforced nanocomposite particles for lithium battery electrodes |
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| KR20160145565A (en) * | 2014-04-14 | 2016-12-20 | 이머리스 그래파이트 앤드 카본 스위춰랜드 리미티드 | Amorphous Carbon Coating of Carbonaceous Particles from Dispersions Including Amphiphilic Organic Compounds |
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| US8580432B2 (en) * | 2008-12-04 | 2013-11-12 | Nanotek Instruments, Inc. | Nano graphene reinforced nanocomposite particles for lithium battery electrodes |
| CN102544459A (en) * | 2012-01-09 | 2012-07-04 | 上海交通大学 | Method for preparing graphene-coated carbon microsphere material by coating graphene oxide on carbon microsphere |
| CN107081127A (en) * | 2017-04-14 | 2017-08-22 | 杭州高烯科技有限公司 | A kind of preparation method of graphene/activated carbon composite porous microspheres |
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