CN112531160A - Amorphous carbon negative electrode material and preparation method and application thereof - Google Patents

Amorphous carbon negative electrode material and preparation method and application thereof Download PDF

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CN112531160A
CN112531160A CN201910886050.7A CN201910886050A CN112531160A CN 112531160 A CN112531160 A CN 112531160A CN 201910886050 A CN201910886050 A CN 201910886050A CN 112531160 A CN112531160 A CN 112531160A
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negative electrode
electrode material
amorphous carbon
carbon negative
reaction
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CN112531160B (en
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胡龙丰
汪福明
徐晓东
任建国
贺雪琴
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BTR New Material Group Co Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection 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
    • H01M4/583Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/05Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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  • Inorganic Chemistry (AREA)
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Abstract

The invention provides an amorphous carbon negative electrode material and a preparation method and application thereof. The amorphous carbon negative electrode material comprises a foam carbon skeleton and carbon particles embedded in the foam carbon skeleton, and the surface of the amorphous carbon negative electrode material comprises macropores and ultramicropores. The preparation method comprises the following steps: (1) reacting carbon particles with an organic complex to obtain sol; (2) adding a curing expanding agent into the sol for reaction to obtain a composite material; (3) and sintering the composite material to obtain the amorphous carbon negative electrode material. The material has a concave-convex structure similar to the lotus leaf surface, and the special structure not only can resist adsorption, but also can provide a rapid diffusion channel for reaction ions, and shows excellent high-rate long-circulation performance in energy storage application.

Description

Amorphous carbon negative electrode material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of energy storage materials, relates to a negative electrode material and a preparation method and application thereof, and particularly relates to an amorphous carbon negative electrode material and a preparation method and application thereof.
Background
Due to the concept of environmental protection and the requirements of consumers, the development of electric vehicles, smart grids, mobile phones, notebook computers and the like increasingly depends on the development of lithium ion batteries. At present, the cathode material of the commercial lithium ion battery is mainly made of carbon materials, the specific capacity is high (200-400 mAh.g < -1 >), and the electrode potential is low (less than 1.0V vs Li)+Li), good cycle performance (over 1000 weeks), stable physical and chemical properties. Carbon materials can be classified into two major types, graphite materials and amorphous carbon materials, according to the degree of crystallization. The graphite material is an ideal lithium battery negative electrode material due to the characteristics of good conductivity, high crystallinity, stable layered structure, suitability for lithium intercalation-deintercalation and the like. At present, the reversible capacity value of the graphite negative electrode material is close to the theoretical capacity value 372mAh/g, the structural stability of the graphite material is poor, the compatibility with electrolyte is poor, and Li+The problems of slow diffusion speed in the ordered layered structure and the like lead to the fact that the traditional graphite cathode material is difficult to meet the requirements of the lithium ion power battery with rapid charging and high-rate discharging. Therefore, amorphous carbon negative electrode materials having high conductivity, and excellent structural stability have been the focus of research.
The amorphous carbon material has a short-range ordered long-range interlaced layered structure, Li+Can be embedded and de-embedded from various angles, shortens the ion diffusion distance, and greatly improves the charge and discharge speed, thereby realizing the rapid charge and discharge of the material. In addition, a large number of micropores and defects exist in the structure of the amorphous material, so that abundant active sites are provided for lithium intercalation, and the reversible capacity is far larger than the theoretical capacity value 372mAh/g of graphite. In addition, amorphous carbon has isotropic structural features and large interlayer spacing, even at low temperatures of-40 ℃ with Li+And the rapid diffusion rate in the electrode can be realized, and the low-temperature performance of the electrode is obviously improved compared with that of a graphite material. Therefore, the amorphous carbon negative electrode material becomes a development trend of the negative electrode material of the power battery in the future. Although amorphous carbon negative electrode materialHas a plurality of advantages, but has a plurality of problems in the application process, such as: (1) the material has more surface defects and larger first irreversible capacity, and reduces the energy density of the battery; (2) abundant active sites on the surface of the material generate side reaction with electrolyte at high temperature, so that the capacity is quickly attenuated; (3) although the amorphous carbon material has more excellent rate capability than the graphite cathode material and can be charged and discharged under the large rate of 20C @1C, the amorphous carbon material has poorer large rate long cycle performance and cannot meet the increasing power requirement of the market; (4) when the material is exposed in the air for a period of time, oxygen-containing functional groups such as-OH, -COOH, -C ═ O and the like in the structure of the material generate chemical adsorption, and impurity gases such as water, oxygen and the like in the air are adsorbed, so that the reversible capacity is sharply reduced. Therefore, the popularization and application of the amorphous carbon material are limited.
In the prior art, there are many processes for improving the performance of negative electrode materials such as graphite, silicon carbon, amorphous carbon and the like, for example, CN105449162 discloses a negative electrode material for a lithium ion battery and a negative electrode sheet thereof, and the proposal proposes that a layer of soft carbon is coated on the surfaces of natural graphite and artificial graphite, so as to partially reduce the irreversible capacity of the original material.
CN109671943A discloses a high-first-efficiency silicon-carbon composite negative electrode material and a preparation method thereof, and the scheme is that a shell similar to SEI components is coated on the surface of a nano silicon by physical vapor deposition and electrochemical deposition to reduce the consumption of lithium ions in the first charge-discharge process.
CN106876710A discloses a soft carbon negative electrode material for a lithium ion battery and a preparation method thereof, and the scheme is that ammonium molybdate and cobalt nitrate are added in a soft carbon precursor raw material to consume simple substance or ionic state sulfur (nitrogen) in a negative electrode, so that the first effect of the material is improved.
CN109148843A discloses a boron-doped negative electrode material with good high-temperature performance and a solid-phase preparation method thereof, in the scheme, a boron-oxygen compound is used as a dopant to improve the graphitization degree of the material by utilizing the catalytic action of boron through surface modification, and on the other hand, boron oxide is compounded with the surface of the negative electrode material to reduce surface defects and reduce side reactions with electrolyte at high temperature.
According to the scheme, the initial coulombic efficiency and the high-temperature performance of the negative electrode material can be effectively improved, but the problem that the performance of the material is greatly reduced due to the fact that the material is adsorbed to impurity gases (water, oxygen and the like) in the air after being placed in the air for a period of time cannot be solved. Particularly, the adsorption reaction mechanism of the amorphous carbon negative electrode material exposed in the air is complex, and the report on improving the adsorbability of the amorphous carbon negative electrode material is few at present, so that the technology for preparing the adsorption-resistant amorphous negative electrode material needs to be developed in an optimized manner.
Disclosure of Invention
In view of the above problems in the prior art, the present invention aims to provide an amorphous carbon negative electrode material, and a preparation method and use thereof. The amorphous carbon negative electrode material provided by the invention has high specific capacity and high-rate charge-discharge cycle retentivity, is strong in adsorption resistance, is excellent in electrochemical performance retention rate when being exposed in air and placed for several days, and effectively solves the problem of performance attenuation of the amorphous carbon negative electrode material after being placed for a long time.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides an amorphous carbon negative electrode material, which comprises a foam carbon skeleton and carbon particles embedded in the foam carbon skeleton, wherein the surface of the amorphous carbon negative electrode material comprises macropores and ultramicropores.
The amorphous carbon negative electrode material provided by the invention is a carbon negative electrode material with high capacity and high rate performance. The material has a three-dimensional hierarchical pore structure: 1) the macroporous structure of the foam type carbon skeleton provides a rapid electrolyte ion transmission channel, which is beneficial to large-current charge and discharge and improves the multiplying power performance; 2) the material has abundant ultramicropore structure on the surface, provides abundant active sites for energy storage reaction, and is beneficial to improving the mass specific capacity of the material; 3) the carbon particle inner core is embedded in the foam type carbon framework to form an integrated self-supporting porous structure, so that the contact internal resistance among carbon particles is reduced, and the electronic conductivity of the material is improved. The amorphous carbon negative electrode material provided by the invention also has adsorption resistance. The surface of the material is provided with dense nanometer-scale ultramicropores, so that a strong capillary effect is generated, and an adsorption energy barrier is increased, thereby reducing the adsorbability of the material.
The foam type carbon skeleton refers to the structure of the carbon skeleton similar to foam carbon, contains a large number of macropores and is in a foam shape. In the present invention, the carbon skeleton of the foam type can be regarded as a carbon skeleton having a carbon foam structure.
The inlaying means that carbon particles enter a foam type carbon skeleton, and the foam type carbon skeleton coats the carbon particles. The foam type carbon skeleton can contain a plurality of carbon particles, namely, the carbon particles (main materials) are connected as bridges.
The following is a preferred technical solution of the present invention, but not a limitation to the technical solution provided by the present invention, and the technical objects and advantageous effects of the present invention can be better achieved and achieved by the following preferred technical solution.
As a preferable technical scheme of the invention, the amorphous carbon negative electrode material has a rough structure. The rough structure refers to the appearance of a material surface similar to concave-convex wrinkles, and the wrinkle appearance describes an ultra-microporous structure developed on the material surface, and the pore diameter of the ultra-microporous structure is less than 1.0 nm. The structure forms 'concave-convex' rough similar to the lotus leaf surface. The rough structure prevents impurity gases in the air from entering the material structure, so that the capacity and the first effect of the material are hardly attenuated after the material is placed in the air.
Preferably, the amorphous carbon anode material is an integrated self-supporting structure. The integration is a single integral structure formed by connecting a foam carbon skeleton and carbon particles through chemical bonding, and the self-supporting is that the three-dimensional structure of the amorphous carbon material is stable, does not need to add a conductive agent, and can be directly used as an electrode.
Preferably, the amorphous carbon negative electrode material has a three-dimensional hierarchical pore structure, wherein the three-dimensional structure refers to a spatial three-dimensional structure, and macropores and ultramicropores are connected with each other. .
In a preferred embodiment of the present invention, the mass of the carbon particles is 70 to 98% of the total mass of the amorphous carbon negative electrode material, for example, 70%, 75%, 80%, 85%, 90%, 95%, or 99%, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned value range are also applicable, and preferably 80 to 95%.
Preferably, the thickness of the foam-type carbon skeleton is 0 to 1.5 μm and does not contain 0, such as 0.1 μm, 0.2 μm, 0.3 μm, 0.4 μm, 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm, 1 μm, 1.1 μm, 1.2 μm, 1.3 μm, 1.4 μm, 1.5 μm, or the like. Here, if the thickness of the foam type carbon skeleton is too thick, the compacted density of the amorphous carbon negative electrode material is reduced, the conductivity is reduced, and the energy density and rate capability are reduced; if the thickness of the foam carbon skeleton is too thin, the coating is not uniform, the carbon particles are exposed, and the effect of reducing the adsorbability of the hard carbon cannot be achieved.
Preferably, the macropores have a pore size of 0.2 to 3 μm, for example 0.2 μm, 0.5 μm, 1 μm, 2 μm or 3 μm, but are not limited to the recited values, and other values not recited in this range are equally applicable.
Preferably, the diameter of the ultramicropores is 0 to 1.0nm excluding 0, for example, 0.2nm, 0.3nm, 0.4nm, 0.5nm, 0.6nm, 0.7nm, 0.8nm, 0.9nm or 1.0nm, but not limited to the values listed, and other values not listed in the numerical range are also applicable, preferably 0 to 0.6nm excluding 0. Here, if the pore diameter of the ultra-micropores is too large, the contact surface between the material and water increases, the capillary action decreases, the hydrophobicity decreases, and the effect of decreasing the adsorbability of the material cannot be achieved; in addition, ultra-micro pores with too large pore diameters increase irreversible reactive sites of the material and the electrolyte, resulting in a decrease in first effect.
Preferably, the total pore volume of the amorphous carbon negative electrode material is 0.5-2.0cm3In g, e.g. 0.5cm3/g、0.8cm3/g、1.0cm3/g、1.2cm3/g、1.5cm3/g、1.8cm3/g、2.0cm3And/g, but are not limited to, the recited values, and other values not recited within the range of values are equally applicable.
Preferably, in the amorphous carbon negative electrode material, the pore volume of the ultra-micropores accounts for 30 to 85% of the total pore volume, for example, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, etc., but is not limited to the enumerated values, and other values not enumerated within the range of the numerical values are also applicable.
Preferably, in the amorphous carbon negative electrode material, the pore volume of the macropores accounts for 13 to 70% of the total pore volume, for example, 13%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, or 70%, but is not limited to the enumerated values, and other unrecited values in the range of the enumerated values are also applicable.
Preferably, the amorphous carbon negative electrode material has a median particle diameter of 8.0 to 40.0 μm, for example, 8.0 μm, 10.0 μm, 14.0 μm, 18.0 μm, 22.0 μm, 26.0 μm, 30.0 μm, 34.0 μm, 38.0 μm, or 40.0 μm, but is not limited to the enumerated values, and other unrecited values within this numerical range are equally applicable, preferably 15.0 to 30.0 μm.
Preferably, the carbon particles have a median particle diameter of 0.2 to 3.0. mu.m, such as 0.2. mu.m, 0.4. mu.m, 0.6. mu.m, 0.8. mu.m, 1.0. mu.m, 1.2. mu.m, 1.4. mu.m, 1.6. mu.m, 1.8. mu.m, 2.0. mu.m, 2.2. mu.m, 2.4. mu.m, 2.6. mu.m, 2.8. mu.m, 3.0. mu.m, or the like. However, the above-mentioned numerical values are not intended to be limiting, and other numerical values not specified in the above-mentioned numerical range are also applicable, and preferably 0.5 to 2.0. mu.m.
Preferably, the specific surface area of the amorphous carbon negative electrode material is 1-50m2G, e.g. 1m2/g、5m2/g、10m2/g、15m2/g、20m2/g、25m2/g、30m2/g、35m2/g、40m2/g、45m2In g or 50m2And/g, but are not limited to the values listed, and other values not listed in the range are equally applicable, preferably 1 to 35m2/g。
Preferably, the powder contact angle of the amorphous carbon negative electrode material with water is 40-85 °, for example, 40 °, 45 °, 50 °, 55 °, 60 °, 65 °, 70 °, 75 °, 80 °, or 85 °, but not limited to the recited values, and other values in the range of the recited values are also applicable. In the invention, the value of the powder contact angle is used for measuring the adsorption capacity of the amorphous carbon negative electrode material to water, and the 0-degree datum line of the value is the powder contact angle between the amorphous carbon negative electrode material and cyclohexane.
In a second aspect, the present invention provides a method for preparing the amorphous carbon negative electrode material according to the first aspect, the method comprising the steps of:
(1) reacting carbon particles with an organic complex to obtain sol;
(2) adding a curing expanding agent into the sol obtained in the step (1) for reaction to obtain a composite material;
(3) and (3) sintering the composite material obtained in the step (2) to obtain the amorphous carbon negative electrode material.
In the preparation method provided by the invention, a three-dimensional foam type graded-hole amorphous carbon negative electrode material is prepared by adding a curing expanding agent by means of a sol-gel auxiliary process, polymerizing at a low temperature and sintering and etching at a high temperature. Specifically, the carbon particles are stirred under the condition of low-temperature heating, the carbon particles with certain sizes and the organic complex compound are subjected to polymerization reaction to form black sticky sol, and then a curing expanding agent is added to play a role in curing so as to realize crosslinking and curing. Meanwhile, the solidified expanding agents are decomposed under the heating condition to generate nanoscale metal oxides and gas micromolecule substances, the gas micromolecules enable the sol to expand and foam to play an expansion role, redundant solvents are removed in a flash drying mode to form a foam type composite material, and the self-supporting three-dimensional hierarchical-pore amorphous carbon material is obtained after high-temperature sintering. Because the nano metal oxide exists in the composite material, the nano metal oxide can react with the carbon matrix material at high temperature to generate an etching effect, and a developed ultramicropore structure, namely a rough structure similar to the lotus leaf surface, is formed on the surface, so that the aim of adsorption resistance is fulfilled. Meanwhile, the metal simple substance generated after the etching reaction can promote the rearrangement of the framework, improve the graphitization degree of the organic complex pyrolytic carbon and improve the first effect.
As a preferable embodiment of the present invention, the carbon particles in the step (1) have a median particle diameter of 0.2 to 3.0. mu.m, for example, 0.2. mu.m, 0.4. mu.m, 0.6. mu.m, 0.8. mu.m, 1.0. mu.m, 1.2. mu.m, 1.4. mu.m, 1.6. mu.m, 1.8. mu.m, 2.0. mu.m, 2.2. mu.m, 2.4. mu.m, 2.6. mu.m, 2.8. mu.m, or 3.0. mu.m. However, the above-mentioned numerical values are not intended to be limiting, and other numerical values not specified in the above-mentioned numerical range are also applicable, and preferably 0.5 to 2.0. mu.m. Here, if the carbon particles are too small, the more macropores are generated in the material, the lower the compaction density, resulting in a lower energy density, and at the same time, the too many pore structures consume a large amount of electrolyte, reducing the first effect; if the carbon particles are too large, the organic complex pyrolytic carbon is not uniformly coated, and even a direct uncoated region appears.
Preferably, the mass ratio of the carbon particles to the organic complex in the step (1) is 1 (0.5-8), such as 1:0.5, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7 or 1:8, and the like, and is preferably 1 (1-6).
In the invention, if the carbon particles are too many relative to the organic complex, the organic complex can not completely wrap the carbon particles into a uniform coating layer and can not be self-assembled into a three-dimensional conductive network structure; if the carbon particles are too small relative to the organic complex, this may result in too much macroporous structure and a lower compacted density.
Preferably, the method for reacting carbon particles with an organic complex according to step (1) comprises: and adding carbon particles into the solution of the organic complex, and heating for reaction to obtain the sol.
Preferably, the organic complex is present in the solution in a mass fraction of 10-90%, for example 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80% or 90%, but not limited to the recited values, and other values not recited within this range are equally applicable, preferably 40-70%. Here, if the concentration is too small, a gel cannot be formed; the organic complex and the carbon particles are difficult to be uniformly mixed when the concentration is overlarge.
Preferably, the organic complex comprises any one of sucrose, starch, gelatin, phenolic novolac resin, polypyrrole, polyaniline or polyvinyl alcohol or a combination of at least two of them. Typical but non-limiting combinations are: sucrose and starch, starch and gelatin, gelatin and phenolic resin thermoplastic, phenolic resin thermoplastic and polypyrrole, polypyrrole and polyaniline, polyaniline and polyvinyl alcohol, and the like. The preferable organic complex can better generate sol effect at low temperature, and contains abundant nitrogen element to improve capacity.
Preferably, the solvent in the solution of the organic complex comprises any one of water, ether, alcohol, ketone or tetrahydrofuran or a combination of at least two thereof.
Preferably, the reaction temperature of the heating reaction is 40 to 100 ℃, for example 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ or 100 ℃, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the reaction time of the heating reaction is 1 to 12 hours, such as 1 hour, 2 hours, 4 hours, 6 hours, 8 hours, 10 hours or 12 hours, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the heating reaction is accompanied by stirring.
Preferably, the heating is performed with an oil bath.
Preferably, the stirring is carried out at a rate of from 10 to 90r/min, for example 10r/min, 20r/min, 30r/min, 40r/min, 50r/min, 60r/min, 70r/min, 80r/min or 90r/min, but not limited to the values listed, and other values not listed in this range of values are equally applicable, preferably from 30 to 60 r/min.
In a preferred embodiment of the present invention, the solidification expanding agent in step (2) includes any one or a combination of at least two of sodium bicarbonate, sodium carbonate, sodium oxalate, and calcium carbonate. The preferable composite salt can play a role in crosslinking and curing and also plays a role in promoting expansion, the composite salt has low decomposition temperature, a large amount of gas micromolecule substances can be generated after decomposition, sol expansion is promoted, the generated nano metal oxide after the composite salt is decomposed can react with a carbon matrix at high temperature to generate the effect of etching and forming micropores, and meanwhile, the reacted metal simple substance promotes the rearrangement of a carbon skeleton, so that the graphitization degree of the organic complex pyrolytic carbon is improved.
Preferably, the mass ratio of the curing expanding agent to the carbon particles in the step (2) is (0.02-0.8): 1, for example, 0.02:1, 0.05:1, 0.08:1, 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1 or 0.8:1, but not limited to the enumerated values, and other non-enumerated values within the numerical range are equally applicable, preferably (0.05-0.5): 1. In the invention, if the addition amount of the curing expanding agent is too much, the curing expanding agent is decomposed to generate a large amount of gas in the curing reaction process, a rich macroporous structure is formed, the inner wall is thinned, and the decomposed product of the curing expanding agent is further etched at high temperature to collapse the porous foam structure; if the addition amount of the curing expanding agent is too small, the crosslinking degree is insufficient, the curing is incomplete, and meanwhile, the gas generated by the decomposition of the curing expanding agent is small, and a porous foam structure cannot be formed.
Preferably, the method for carrying out the reaction of step (2) comprises: and adding a curing expanding agent, mixing, stopping mixing, carrying out heating reaction, and drying after reaction to obtain the composite material. Here, the mixing operation (e.g., the stirring mixing operation) is stopped during the heating reaction because the mixing operation may hinder the curing of the composite material while destroying the three-dimensional hierarchical pore structure formed by the crosslinking reaction.
Preferably, the method of mixing is stirring mixing.
Preferably, the stirring rate of the stirring is 10 to 90r/min, such as 10r/min, 20r/min, 30r/min, 40r/min, 50r/min, 60r/min, 70r/min, 80r/min or 90r/min, but is not limited to the recited values, and other non-recited values within this range of values are equally applicable, preferably 30 to 60 r/min.
Preferably, the mixing time is 0.5 to 3 hours, such as 0.5 hours, 1 hour, 2 hours, 3 hours, etc., but is not limited to the recited values, and other values not recited within the range of values are equally applicable.
Preferably, the reaction temperature of the heating reaction is 60 to 300 ℃, for example, 60 ℃, 100 ℃, 150 ℃, 200 ℃, 250 ℃ or 300 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the reaction time of the heating reaction is 0.5 to 10 hours, such as 0.5 hour, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, or 10 hours, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the drying method is cooling drying or supercritical drying. Here, it is preferred that both flash drying modes rapidly remove excess solvent and maintain the three-dimensional foam structure of the lysogen.
In a preferred embodiment of the present invention, the sintering in step (3) is performed in a protective atmosphere.
Preferably, the protective atmosphere includes any one of a nitrogen atmosphere, a helium atmosphere, a neon atmosphere, an argon atmosphere, or a xenon atmosphere, or a combination of at least two thereof.
Preferably, the sintering temperature in step (3) is 600-1500 ℃, such as 600 ℃, 700 ℃, 800 ℃, 900 ℃, 1000 ℃, 1100 ℃, 1200 ℃, 1300 ℃, 1400 ℃ or 1500 ℃, but not limited to the recited values, and other unrecited values within the range of values are equally applicable.
Preferably, the sintering time in step (3) is 0.5-6h, such as 0.5h, 1h, 2h, 3h, 4h, 5h or 6h, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the temperature increase rate of the sintering in step (3) is 1-30 deg.C/min, such as 1 deg.C/min, 3 deg.C/min, 5 deg.C/min, 7 deg.C/min, 10 deg.C/min, 13 deg.C/min, 15 deg.C/min, 17 deg.C/min, 20 deg.C/min, or 30 deg.C/min, but is not limited to the values listed, and other values not listed in this range of values are equally applicable, preferably 1-15 deg.C/min.
Preferably, the sintering reactor in step (3) comprises any one of a vacuum furnace, a box furnace, a tube furnace, a roller kiln, a pushed slab kiln, a microwave pyrolysis furnace or an ultraviolet pyrolysis furnace or a combination of at least two of the above.
Preferably, step (3) further comprises: and cooling to 15-35 ℃ after sintering, namely cooling to room temperature.
Preferably, step (3) further comprises: and purifying the product obtained after sintering. In the present invention, the purification is aimed at removing impurities of metal salts generated during the reaction.
Preferably, the method of purification comprises: and stirring and mixing the sintered product with acid, performing suction filtration, washing the obtained solid to be neutral by using water, centrifuging and drying, and demagnetizing and screening the dried product to obtain the amorphous carbon negative electrode material.
Preferably, the mass ratio of the product obtained after sintering to the acid is from 1:2 to 1:50, for example 1:2, 1:5, 1:10, 1:15, 1:20, 1:25, 1:30, 1:35, 1:40, 1:45 or 1:50, but is not limited to the recited values, and other values not recited within this range of values are equally applicable, preferably from 1:5 to 1: 20.
Preferably, the acid comprises any one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid, or oxalic acid, or a combination of at least two thereof.
Preferably, the acid is present in a concentration of 1 to 5mol/L, such as 1.0mol/L, 1.5mol/L, 2.0mol/L, 2.5mol/L, 3.0mol/L, 3.5mol/L, 4.0mol/L, 4.5mol/L, or 5.0mol/L, but not limited to the recited values, and other values not recited within the range of values are equally applicable.
Preferably, the mixing time is 0.5 to 10 hours, such as 0.5 hour, 1.0 hour, 2.0 hours, 3.0 hours, 4.0 hours, 5.0 hours, 6.0 hours, 7.0 hours, 8.0 hours, 9.0 hours, or 10.0 hours, but is not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the centrifugation is carried out for a period of time of 0.5 to 8 hours, such as 0.5 hour, 1.0 hour, 2.0 hours, 3.0 hours, 4.0 hours, 5.0 hours, 6.0 hours, 7.0 hours, 8.0 hours, etc., but not limited to the recited values, and other values not recited within this range of values are equally applicable, preferably 1.5 to 5 hours.
Preferably, the drying is carried out in a vacuum drying oven, a forced air drying oven, a box oven, a rotary kiln or a double cone dryer.
Preferably, the drying temperature is 50-200 ℃, such as 50 ℃, 80 ℃, 100 ℃, 120 ℃, 150 ℃, 180 ℃ or 200 ℃, but not limited to the recited values, and other values not recited within the range of values are equally applicable, preferably 80-150 ℃.
Preferably, the drying time is 5-48h, such as 5h, 10h, 15h, 20h, 25h, 30h, 35h, 40h or 48h, but not limited to the recited values, and other values not recited in the range of values are equally applicable.
As a preferable technical scheme of the invention, the preparation method of the carbon particles in the step (1) comprises the following steps: and carbonizing the carbon precursor in a protective atmosphere to obtain the carbon particles.
Preferably, the protective atmosphere includes any one of a nitrogen atmosphere, a helium atmosphere, a neon atmosphere, an argon atmosphere, or a xenon atmosphere, or a combination of at least two thereof.
Preferably, the carbon precursor comprises any one of biomass, resin, pitch or char, or a combination of at least two of the foregoing.
Preferably, the biomass comprises any one of coconut shells, apricot shells, fruit shells or walnut shells or a combination of at least two of the same.
Preferably, the resin comprises any one of furfural resin, phenol resin, melamine formaldehyde resin, epoxy resin, unsaturated polyester, vinyl ester, bismaleimide resin, polyimide resin, polyethylene, polyvinyl chloride, Polystyrene (PS), polypropylene, or acrylonitrile-styrene-butadiene copolymer (ABS), or a combination of at least two thereof.
Preferably, the bitumen comprises any one of coal tar bitumen, shale bitumen or petroleum bitumen, or a combination of at least two of these.
Preferably, the coke comprises any one of coal coke, petroleum coke, or mesocarbon microbeads, or a combination of at least two of the foregoing.
Preferably, the carbonization temperature is 300-850 ℃, such as 300 ℃, 400 ℃, 500 ℃, 600 ℃, 700 ℃, 800 ℃ or 850 ℃, but not limited to the recited values, and other unrecited values within the range of values are equally applicable.
Preferably, the carbonization time is 0.5 to 8h, such as 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, 7h or 8h, but not limited to the recited values, and other values not recited within the range of values are equally applicable.
Preferably, the temperature increase rate of the carbonization is 1 to 10 ℃/min, for example, 1 ℃/min, 2 ℃/min, 4 ℃/min, 6 ℃/min, 7 ℃/min, 8 ℃/min, or 10 ℃/min, and the like, but is not limited to the recited values, and other values not recited within the range of the values are also applicable.
Preferably, the preparation method of the carbon particle further comprises the following steps: and crushing the product obtained after carbonization.
As a further preferable technical scheme of the preparation method, the method comprises the following steps:
(1) heating the carbon precursor to 850 ℃ at the heating rate of 1-10 ℃/min under the protective atmosphere for carbonization, wherein the carbonization time is 0.5-8h, cooling to 15-35 ℃ after carbonization, and crushing the product obtained after carbonization to obtain carbon particles;
(2) adding carbon particles into the solution of the organic complex, heating and reacting under stirring at the reaction temperature of 40-100 ℃ for 1-12h to obtain sol;
the carbon particle has a median particle diameter of 0.5-2.0 μm, the mass ratio of the carbon particle to the organic complex is 1 (1-6), and the mass fraction of the organic complex in the organic complex solution is 40-70%;
(3) adding a curing expanding agent into the sol obtained in the step (2), stirring and mixing for 0.5-3h, stopping stirring, heating and reacting at 60-300 ℃ for 0.5-10h, and drying after reaction to obtain a composite material;
wherein the curing expanding agent is any one or the combination of at least two of sodium bicarbonate, sodium carbonate, sodium oxalate or calcium carbonate, and the mass ratio of the curing expanding agent to the carbon particles is (0.05-0.5) to 1; the drying method is cooling drying or supercritical drying;
(4) heating the composite material obtained in the step (3) to 600-1500 ℃ at the heating rate of 1-15 ℃/min under the protective atmosphere, sintering for 0.5-6h, cooling to 15-35 ℃ after sintering, stirring and mixing the product obtained after sintering and acid with the concentration of 1-5mol/L for 0.5-10h according to the mass ratio of 1:5-1:20, carrying out suction filtration, washing the obtained solid to be neutral by using water, then centrifuging for 1.5-5h, drying for 5-48h at the temperature of 80-150 ℃, and demagnetizing and screening the dried product to obtain the amorphous carbon negative electrode material.
In the further preferable technical scheme, the preferable curing expanding agent is added in the sol reaction, the curing expanding agent is decomposed at low temperature to generate a large amount of micromolecular gas substances for foaming expansion, in the high-temperature sintering process, the nano metal oxide generated by decomposition of the curing expanding agent can be used as an activating agent for etching and pore-forming, meanwhile, the metal simple substance obtained after the reaction can also promote rearrangement of a carbon skeleton, improve the graphitization degree of the organic complex pyrolytic carbon, and after acid purification and impurity removal are added, the three-dimensional foam amorphous carbon negative electrode material is prepared, so that a concave-convex structure similar to the lotus leaf surface is formed.
In a third aspect, the present invention provides a use of the amorphous carbon negative electrode material according to the first aspect, for a lithium ion battery, a sodium ion battery or a supercapacitor.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention uses organic complex as a coating carbon source to form a foam type carbon skeleton, uses compound salt as a curing expanding agent, successfully designs an amorphous carbon negative electrode material which uses carbon particles as a core and is embedded in the foam type carbon skeleton to form an integrated self-supporting three-dimensional hierarchical pore structure through a simple process of sol polymerization reaction and high-temperature heat treatment, the surface of the material contains abundant ultramicropores, the material is similar to the 'concave-convex' rough surface on the surface of lotus leaves, and the material has strong adsorption resistance.
(2) The amorphous carbon negative electrode material provided by the invention has a special three-dimensional hierarchical pore structure, wherein: a. the macroporous foam structure provides an electrolyte ion rapid transmission channel, which is beneficial to large-current charging and discharging, and the retention rate of lithium intercalation capacity can reach 92.2 percent under the current density of 5C @5C after 3000 times of circulation, which is superior to the level of the existing amorphous carbon material (about 86 percent in 3C @3C 800 weeks); b. the surface of the amorphous carbon material is formed with an ultra-microporous 'rough' structure similar to lotus leaf development, the specific mass capacity of the material is improved, the first lithium removal capacity can reach 509.7mAh/g, the first coulombic efficiency can reach 84.6%, the adsorbability of the material can be reduced, the powder contact angle of the material can be increased to 78 degrees from 55 degrees, the prepared amorphous carbon material can be placed in the air for 30 days, the reversible capacity and the first coulombic efficiency are almost unchanged, the amorphous carbon material is far superior to the level of the existing amorphous carbon material (the capacity retention rate is about 90% after the amorphous carbon material is placed for 30 days), and the problem of placing attenuation of the amorphous carbon material in the air is remarkably improved.
(3) The preparation method provided by the invention has the advantages of simple operation process, easily obtained raw materials, environmental friendliness, controllable appearance of the obtained amorphous carbon negative electrode material and easiness in large-scale production.
Drawings
FIG. 1 is a scanning electron microscope picture of an amorphous carbon negative electrode material prepared in example 1 of the present invention;
FIG. 2(a) is a nitrogen adsorption curve of an amorphous carbon negative electrode material prepared in example 1 of the present invention;
FIG. 2(b) is a pore size distribution curve of the amorphous carbon negative electrode material prepared in example 1 of the present invention;
FIG. 3 is a graph showing the conductivity of an amorphous carbon negative electrode material prepared in example 1 of the present invention;
FIG. 4 is a first charge-discharge curve of the amorphous carbon negative electrode material prepared in example 1 of the present invention;
fig. 5 is a cycle performance curve of the amorphous carbon negative electrode material prepared in example 1 of the present invention.
Detailed Description
In order to better illustrate the present invention and facilitate the understanding of the technical solutions of the present invention, the present invention is further described in detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
The following are typical but non-limiting examples of the invention:
example 1
The example prepares the adsorption-resistant amorphous carbon negative electrode material according to the following method:
(1) placing 800g of coconut shells in a box furnace under nitrogen atmosphere, heating to 500 ℃ at a heating rate of 5 ℃/min, carbonizing for 6h, cooling to 25 ℃ to obtain 220g of carbonized material, crushing by using a ball mill, and crushing the median particle size of the material to 1.5 mu m to obtain carbon particles;
(2) adding 100g of carbon particles into 500g of 60% gelatin aqueous solution, placing the mixture in an oil bath pan with a magnetic stirrer, heating to 60 ℃, and stirring for 8 hours to form uniformly mixed sticky sol;
(3) adding 50g of sodium bicarbonate into the viscous sol, continuing stirring for 2h, stopping stirring, raising the temperature to 130 ℃, preserving the temperature for 4h, performing expansion reaction, and performing freeze drying to obtain 420g of three-dimensional foam type composite material;
(4) putting 420g of the three-dimensional foam type composite material into a graphite crucible, placing the graphite crucible into a box furnace, introducing nitrogen protective gas, heating to 1300 ℃ at the heating rate of 5 ℃/min, preserving heat for 4h, cooling to room temperature, and taking out to obtain 140g of black mixture;
(5) and (3) crushing the mixture obtained in the step (4), mixing the crushed mixture with 3mol/L diluted hydrochloric acid according to a mass ratio of 1:10, soaking for 4 hours, then centrifugally washing to be neutral, placing the mixture in a 100 ℃ oven for drying for 12 hours, and then removing magnetism and screening the dried material to obtain the anti-adsorption amorphous carbon negative electrode material.
The structure test of the adsorption-resistant amorphous carbon negative electrode material prepared in the embodiment is carried out by the following method:
the specific surface area of the material was tested using a Tristar3000 full-automatic specific surface area and porosity analyzer from Michner instruments USA.
The particle size range of the material and the average particle size of the raw material particles were measured using a malvern laser particle size tester MS 2000.
The surface appearance, particle size and the like of the sample were observed by a scanning electron microscope of Hitachi S4800.
The amorphous carbon negative electrode material prepared by the embodiment comprises a foam carbon skeleton and carbon particles embedded in the foam carbon skeleton, and the surface of the amorphous carbon negative electrode material comprises macropores and ultramicropores. The amorphous carbon negative electrode material has an integrated self-supporting structure and a three-dimensional hierarchical pore structure. The amorphous carbon negative electrode material has a rough structure.
In the amorphous carbon negative electrode material prepared in this embodiment, the mass of carbon particles accounts for 82% of the total mass of the amorphous carbon negative electrode material, the thickness of the foam carbon skeleton is 1.0 μm, the pore diameter of macropores is 0.2-2 μm, and the pore diameter of ultramicropores is below 0.6 nm; the total pore volume of the amorphous carbon negative electrode material is 1.8cm3The volume of the ultramicropores accounts for 70 percent of the total pore volume, and the volume of the macropores accounts for 28 percent of the total pore volume; the median particle diameter (D50) of the amorphous carbon negative electrode material is 21.388 mu m, and the specific surface area is 22.5m2And the powder contact angle of the amorphous carbon negative electrode material and water is 61 degrees (the powder contact angle between the amorphous carbon negative electrode material and cyclohexane is a datum line of 0 degrees).
The electrochemical test and the absorption performance decay test results of the amorphous carbon negative electrode material prepared in the embodiment are shown in table 1.
Fig. 1 is a scanning electron microscope picture of the amorphous carbon negative electrode material prepared in this embodiment, and it can be seen from the picture that the particle surface of the amorphous carbon negative electrode material is uneven, has a rich macroporous structure, and has a particle size of about 21 um.
Fig. 2(a) is a nitrogen adsorption curve of the amorphous carbon negative electrode material prepared in this example, fig. 2(b) is a pore size distribution curve of the amorphous carbon negative electrode material prepared in this example, it can be seen from the graph (a) that the allelic curve of the material is an isotherm of type iv, the adsorption amount rapidly increases in the region near P/P0 of 0.1, corresponding to capillary adsorption of ultra-micropores, and when P/P0 continues to increase to near 1, the adsorption is saturated and the curve is flat, which indicates that a microporous structure mainly exists in the material; as can be seen from the figure (b), the pore diameters of the material structure are mainly distributed in the range of 0.3-0.6nm and belong to ultramicropores;
FIG. 3 is a graph showing the conductivity curve of the amorphous carbon negative electrode material prepared in this example, which is a conductivity tester Mitsubishi chemical MCP-PD 51. from this graph, it can be seen that the amorphous carbon negative electrode material shows an electron conductivity of 62.5S/cm under a pressure of 60 MPa;
FIG. 4 is a first charge-discharge curve of the amorphous carbon negative electrode material prepared in this example, from which it can be seen that the lithium deintercalation capacity of the amorphous carbon negative electrode material is 570mAh/g and 482.1mAh/g, respectively;
fig. 5 is a cycle performance curve of the amorphous carbon negative electrode material prepared in this example, and it can be seen from the curve that the capacity retention rate of the amorphous carbon negative electrode material is close to 87.6% after 3000 cycles of 5C high-rate charge and discharge.
Example 2
The example prepares the adsorption-resistant amorphous carbon negative electrode material according to the following method:
(1) placing 600g of asphalt in a box furnace in nitrogen atmosphere, heating to 650 ℃ at a heating rate of 3 ℃/min, carbonizing for 4h, cooling to 25 ℃ to obtain 200g of carbonized material, crushing by using a ball mill, and crushing the median particle size of the material to 1.0 mu m to obtain carbon particles;
(2) adding 200g of carbon particles into 250g of 40 mass percent thermoplastic phenolic resin alcoholic solution, placing the solution in an oil bath pot with a magnetic stirrer, heating the solution to 55 ℃, and stirring the solution for 10 hours to form uniformly mixed sticky sol;
(3) adding 60g of sodium oxalate into the viscous sol, continuing stirring for 3 hours, stopping stirring, raising the temperature to 260 ℃, preserving the temperature for 4 hours, and after an expansion reaction, performing freeze drying to obtain 330g of a three-dimensional foam type composite material;
(4) putting 330g of the three-dimensional foam type composite material into a graphite crucible, placing the graphite crucible into a box furnace, introducing argon protective gas, heating to 1100 ℃ at the heating rate of 2 ℃/min, preserving heat for 3h, cooling to room temperature, and taking out to obtain 240g of black mixture;
(5) and (3) crushing the mixture obtained in the step (4), mixing the crushed mixture with 1mol/L dilute sulfuric acid according to a mass ratio of 1:15, soaking for 3 hours, then centrifugally washing to be neutral, placing the mixture in a 120 ℃ oven for drying for 10 hours, and then removing magnetism and screening the dried material to obtain the anti-adsorption amorphous carbon negative electrode material.
The amorphous carbon negative electrode material obtained in this example was subjected to a structural test by the method of example 1:
the amorphous carbon negative electrode material prepared by the embodiment comprises a foam carbon skeleton and carbon particles embedded in the foam carbon skeleton, and the surface of the amorphous carbon negative electrode material comprises macropores and ultramicropores. The amorphous carbon negative electrode material has an integrated self-supporting structure and a three-dimensional hierarchical pore structure. The amorphous carbon negative electrode material has a rough structure.
In the amorphous carbon negative electrode material prepared in this embodiment, the mass of carbon particles accounts for 88% of the total mass of the amorphous carbon negative electrode material, the thickness of the foam carbon skeleton is 0.6 μm, the pore diameter of macropores is 0.4-3 μm, and the pore diameter of ultramicropores is ultramicropores<0.83 nm; the total pore volume of the amorphous carbon negative electrode material is 1.841cm3The volume of the ultramicropores accounts for 68.5 percent of the total pore volume, and the macropores account for 29.7 percent of the total pore volume; the median particle diameter (D50) of the amorphous carbon negative electrode material is 15.284 mu m, and the specific surface area is 38.2m2And the powder contact angle of the amorphous carbon negative electrode material and water is 52 degrees (the powder contact angle between the amorphous carbon negative electrode material and cyclohexane is a datum line of 0 degrees).
The electrochemical test and the absorption performance decay test results of the amorphous carbon negative electrode material prepared in the embodiment are shown in table 1.
Example 3
The example prepares the adsorption-resistant amorphous carbon negative electrode material according to the following method:
(1) placing 800g of apricot shells in a box furnace under nitrogen atmosphere, heating to 500 ℃ at a heating rate of 5 ℃/min, carbonizing for 6h, cooling to 25 ℃ to obtain a carbonized material, crushing by using a ball mill, and crushing the median particle size of the material to 0.5 mu m to obtain carbon particles;
(2) adding 100g of carbon particles into 860g of gelatin aqueous solution with the mass fraction of 70%, placing the mixture in an oil bath pan with a mechanical stirrer, heating the mixture to 60 ℃, stirring the mixture for 8 hours at 30r/min, and forming uniformly mixed sticky sol;
(3) adding 5g of calcium carbonate into the viscous sol, continuing stirring for 2 hours at 30r/min, stopping stirring, raising the temperature to 130 ℃, preserving the heat for 4 hours, performing expansion reaction, and performing freeze drying to obtain a three-dimensional foam type composite material;
(4) putting the three-dimensional foam type composite material into a graphite crucible, placing the graphite crucible into a box-type furnace, introducing nitrogen protective gas, heating to 1300 ℃ at the heating rate of 5 ℃/min, preserving heat for 4h, cooling to room temperature, and taking out to obtain a black mixture;
(5) and (3) crushing the mixture obtained in the step (4), stirring and mixing the crushed mixture with 3mol/L diluted hydrochloric acid according to the mass ratio of 1:5, soaking for 4 hours, then centrifugally washing to be neutral, placing the mixture in an oven at 80 ℃ for drying for 12 hours, and then removing magnetism and screening the dried material to obtain the anti-adsorption amorphous carbon negative electrode material.
The amorphous carbon negative electrode material obtained in this example was subjected to a structural test by the method of example 1:
the amorphous carbon negative electrode material prepared by the embodiment comprises a foam carbon skeleton and carbon particles embedded in the foam carbon skeleton, and the surface of the amorphous carbon negative electrode material comprises macropores and ultramicropores. The amorphous carbon negative electrode material has an integrated self-supporting structure and a three-dimensional hierarchical pore structure. The amorphous carbon negative electrode material has a rough structure.
In the amorphous carbon negative electrode material prepared in this embodiment, the mass of carbon particles accounts for 92% of the total mass of the amorphous carbon negative electrode material, the thickness of the foam carbon skeleton is 1.2 μm, the pore diameter of macropores is 0.2-2 μm, and the pore diameter of ultramicropores is ultramicropores<0.72 nm; the total pore volume of the amorphous carbon negative electrode material is 1.077cm3The volume of the ultramicropores accounts for 85.0 percent of the total pore volume, and the volume of the macropores accounts for 13.2 percent of the total pore volume; the median particle diameter (D50) of the amorphous carbon negative electrode material is 11.374 mu m, and the specific surface area is 8.9m2And the powder contact angle of the amorphous carbon negative electrode material and water is 78 degrees (the powder contact angle between the amorphous carbon negative electrode material and cyclohexane is a datum line of 0 degrees). .
The electrochemical test and the absorption performance decay test results of the amorphous carbon negative electrode material prepared in the embodiment are shown in table 1.
Example 4
The example prepares the adsorption-resistant amorphous carbon negative electrode material according to the following method:
(1) placing 800g of walnut shells in a box furnace under nitrogen atmosphere, heating to 500 ℃ at a heating rate of 5 ℃/min, carbonizing for 6h, cooling to 25 ℃ to obtain a carbonized material, crushing by using a ball mill, and crushing the median particle size of the material to 2.0 mu m to obtain carbon particles;
(2) adding 100g of carbon particles into 200g of starch water solution with the mass fraction of 50%, placing the mixture in an oil bath pan with a mechanical stirrer, heating the mixture to 60 ℃, and stirring the mixture for 8 hours at 60r/min to form uniformly mixed sticky sol;
(3) adding 30g of sodium carbonate into the viscous sol, continuing stirring for 2 hours at the speed of 60r/min, stopping stirring, raising the temperature to 130 ℃, preserving the temperature for 4 hours, performing expansion reaction, and performing freeze drying to obtain a three-dimensional foam type composite material;
(4) putting the three-dimensional foam type composite material into a graphite crucible, placing the graphite crucible into a box-type furnace, introducing nitrogen protective gas, heating to 1300 ℃ at the heating rate of 5 ℃/min, preserving heat for 4h, cooling to room temperature, and taking out to obtain a black mixture;
(5) and (3) crushing the mixture obtained in the step (4), stirring and mixing the crushed mixture with 3mol/L diluted hydrochloric acid according to the mass ratio of 1:20, soaking for 4 hours, then centrifugally washing to be neutral, placing the mixture in a 150 ℃ oven for drying for 8 hours, and then removing magnetism and screening the dried material to obtain the anti-adsorption amorphous carbon negative electrode material.
The amorphous carbon negative electrode material obtained in this example was subjected to a structural test by the method of example 1:
the amorphous carbon negative electrode material prepared by the embodiment comprises a foam carbon skeleton and carbon particles embedded in the foam carbon skeleton, and the surface of the amorphous carbon negative electrode material comprises macropores and ultramicropores. The amorphous carbon negative electrode material has an integrated self-supporting structure and a three-dimensional hierarchical pore structure. The amorphous carbon negative electrode material has a rough structure.
In the amorphous carbon negative electrode material prepared in this embodiment, the mass of carbon particles accounts for 92% of the total mass of the amorphous carbon negative electrode material, and the foam carbon skeletonHas a thickness of 1.2 μm, a pore diameter of the macropores of 0.2-2 μm, and a pore diameter of the ultramicropores of<0.72 nm; the total pore volume of the amorphous carbon negative electrode material is 1.077cm3The volume of the ultramicropores accounts for 85.0 percent of the total pore volume, and the volume of the macropores accounts for 13.2 percent of the total pore volume; the median particle diameter (D50) of the amorphous carbon negative electrode material is 11.374 mu m, and the specific surface area is 8.9m2And the powder contact angle of the amorphous carbon negative electrode material and water is 78 degrees (the powder contact angle between the amorphous carbon negative electrode material and cyclohexane is a datum line of 0 degrees).
The electrochemical test and the absorption performance decay test results of the amorphous carbon negative electrode material prepared in the embodiment are shown in table 1.
Example 5
The example prepares the adsorption-resistant amorphous carbon negative electrode material according to the following method:
(1) placing 800g of walnut shells in a box furnace under nitrogen atmosphere, heating to 300 ℃ at a heating rate of 1 ℃/min, carbonizing for 8h, cooling to 25 ℃ to obtain a carbonized material, crushing by using a ball mill, and crushing the median particle size of the material to 0.2 mu m to obtain carbon particles;
(2) adding 100g of carbon particles into 890g of a polyvinyl alcohol aqueous solution with the mass fraction of 90%, placing the mixture in an oil bath pot with a mechanical stirrer, heating the mixture to 40 ℃, stirring the mixture for 12 hours at a speed of 10r/min, and forming uniformly mixed sticky sol;
(3) adding 80g of sodium carbonate into the viscous sol, continuing stirring for 0.5h at 10r/min, stopping stirring, raising the temperature to 60 ℃, preserving the temperature for 8h, performing expansion reaction, and performing freeze drying to obtain a three-dimensional foam type composite material;
(4) putting the three-dimensional foam type composite material into a graphite crucible, placing the graphite crucible into a box-type furnace, introducing nitrogen protective gas, heating to 600 ℃ at the heating rate of 1 ℃/min, preserving heat for 6 hours, cooling to room temperature, and taking out to obtain a black mixture;
(5) and (3) crushing the mixture obtained in the step (4), mixing the crushed mixture with 2mol/L diluted hydrochloric acid according to a mass ratio of 1:2, soaking for 10 hours, then centrifugally washing to be neutral, placing the mixture in a 50 ℃ oven for drying for 48 hours, and then removing magnetism and screening the dried material to obtain the anti-adsorption amorphous carbon negative electrode material.
The amorphous carbon negative electrode material obtained in this example was subjected to a structural test by the method of example 1:
the amorphous carbon negative electrode material prepared by the embodiment comprises a foam carbon skeleton and carbon particles embedded in the foam carbon skeleton, and the surface of the amorphous carbon negative electrode material comprises macropores and ultramicropores. The amorphous carbon negative electrode material has an integrated self-supporting structure and a three-dimensional hierarchical pore structure. The amorphous carbon negative electrode material has a rough structure.
In the amorphous carbon negative electrode material prepared in this embodiment, the mass of carbon particles accounts for 70.1% of the total mass of the amorphous carbon negative electrode material, the thickness of the foam carbon skeleton is 1.5 μm, the pore diameter of macropores is 0.3-2 μm, and the pore diameter of ultramicropores is ultramicropores<0.54 nm; the total pore volume of the amorphous carbon negative electrode material is 2.044cm3The volume of the ultramicropores accounts for 28.9 percent of the total pore volume, and the macropores account for 70.1 percent of the total pore volume; the median particle diameter (D50) of the amorphous carbon negative electrode material is 8.132 mu m, and the specific surface area is 50.1m2And the powder contact angle of the amorphous carbon negative electrode material and water is 47 degrees (the powder contact angle between the amorphous carbon negative electrode material and cyclohexane is a datum line of 0 degrees).
The electrochemical test and the absorption performance decay test results of the amorphous carbon negative electrode material prepared in the embodiment are shown in table 1.
Example 6
The example prepares the adsorption-resistant amorphous carbon negative electrode material according to the following method:
(1) placing 900g of coconut shells in a box furnace under nitrogen atmosphere, heating to 850 ℃ at a heating rate of 10 ℃/min, carbonizing for 0.5h, cooling to 25 ℃ to obtain a carbonized material, crushing by using a ball mill, and crushing the median particle size of the material to 3.0 mu m to obtain carbon particles;
(2) adding 100g of carbon particles into 500g of polyvinyl alcohol aqueous solution with the mass fraction of 10%, placing the mixture in an oil bath pot with a mechanical stirrer, heating the mixture to 100 ℃, and stirring the mixture for 1 hour at 90r/min to form uniformly mixed sticky sol;
(3) adding 2g of sodium carbonate into the viscous sol, continuing stirring for 2 hours at 90r/min, stopping stirring, raising the temperature to 300 ℃, preserving the temperature for 0.5 hour, performing expansion reaction, and performing freeze drying to obtain a three-dimensional foam type composite material;
(4) putting the three-dimensional foam type composite material into a graphite crucible, placing the graphite crucible into a box-type furnace, introducing nitrogen protective gas, heating to 1500 ℃ at the heating rate of 30 ℃/min, preserving heat for 0.5h, cooling to room temperature, and taking out to obtain a black mixture;
(5) and (3) crushing the mixture obtained in the step (4), stirring and mixing the crushed mixture with 5mol/L diluted hydrochloric acid according to the mass ratio of 1:50, soaking for 0.5h, then centrifugally washing to be neutral, drying in a 200 ℃ oven for 5h, and then demagnetizing and screening the dried material to obtain the anti-adsorption amorphous carbon negative electrode material.
The amorphous carbon negative electrode material obtained in this example was subjected to a structural test by the method of example 1:
the amorphous carbon negative electrode material prepared by the embodiment comprises a foam carbon skeleton and carbon particles embedded in the foam carbon skeleton, and the surface of the amorphous carbon negative electrode material comprises macropores and ultramicropores. The amorphous carbon negative electrode material has an integrated self-supporting structure and a three-dimensional hierarchical pore structure. The amorphous carbon negative electrode material has a rough structure.
In the amorphous carbon negative electrode material prepared in this embodiment, the mass of carbon particles accounts for 85% of the total mass of the amorphous carbon negative electrode material, the thickness of the foam carbon skeleton is 0.5 μm, the pore diameter of macropores is 0.2-1 μm, and the pore diameter of ultramicropores is ultramicropores<0.49 nm; the total pore volume of the amorphous carbon negative electrode material is 0.532cm3The volume of the ultramicropores accounts for 84.3 percent of the total pore volume, and the volume of the macropores accounts for 15.4 percent of the total pore volume; the median particle diameter (D50) of the amorphous carbon negative electrode material is 39.873 mu m, and the specific surface area is 1.04m2And the powder contact angle of the amorphous carbon negative electrode material and water is 85 degrees (the powder contact angle between the amorphous carbon negative electrode material and cyclohexane is a datum line of 0 degrees).
The electrochemical test and the absorption performance decay test results of the amorphous carbon negative electrode material prepared in the embodiment are shown in table 1.
Example 7
The raw materials and operating conditions for the various steps of this example were the same as in example 1, except that only 1g of sodium bicarbonate was added in step (3).
The amorphous carbon negative electrode material obtained in this example was subjected to a structural test by the method of example 1:
the amorphous carbon negative electrode material prepared by the embodiment comprises a foam carbon skeleton and carbon particles embedded in the foam carbon skeleton, and the surface of the amorphous carbon negative electrode material only contains a small amount of macropores and ultramicropores.
In the amorphous carbon negative electrode material prepared in this embodiment, the mass of carbon particles accounts for 82% of the total mass of the amorphous carbon negative electrode material, the thickness of the foam carbon skeleton is 2.3 μm, the pore diameter of macropores is 0.1-1 μm, and the pore diameter of ultramicropores is ultramicropores<0.42 nm; the total pore volume of the amorphous carbon negative electrode material is 0.132cm3The volume of the ultramicropores accounts for 98.3 percent of the total pore volume, and the volume of the macropores accounts for 1.3 percent of the total pore volume; the median particle diameter (D50) of the amorphous carbon negative electrode material is 38.735 mu m, and the specific surface area is 3.6m2And the powder contact angle of the amorphous carbon negative electrode material and water is 67 degrees (the datum line of the powder contact angle between the amorphous carbon negative electrode material and cyclohexane is 0 degrees).
The electrochemical test and the absorption performance decay test results of the amorphous carbon negative electrode material prepared in the embodiment are shown in table 1.
Example 8
The raw materials and operating conditions for the various steps of this example were the same as in example 1, except that 90g of sodium bicarbonate was added in step (3).
The amorphous carbon negative electrode material obtained in this example was subjected to a structural test by the method of example 1:
the amorphous carbon negative electrode material prepared by the embodiment comprises a carbon coating layer with a porous structure and a carbon particle core, wherein the surface of the amorphous carbon negative electrode material comprises micropores (containing ultramicropores smaller than 1 nm) with the diameter of 2nm, mesopores with the diameter of 2-5 nm and macropores, and the proportion of the macropores is very small.
In the amorphous carbon negative electrode material prepared in this embodiment, the mass of carbon particles accounts for 96% of the total mass of the amorphous carbon negative electrode material, the thickness of the coating layer is 0.3 μm, the pore diameter of macropores is 0.2-3 μm, and the pore diameter of micropores is mainly distributed at 0.3-5.0nm (including ultramicropores); the total pore volume of the amorphous carbon negative electrode material is 0.527cm3Per g, wherein<The pore volume of the 2nm micropores accounts for 63.4% of the total pore volume, and the macropores account for 1.9% of the total pore volume; the median particle diameter (D50) of the amorphous carbon negative electrode material is 39.453 mu m, and the specific surface area is 86m2And the powder contact angle of the amorphous carbon negative electrode material and water is 48 degrees (the powder contact angle between the amorphous carbon negative electrode material and cyclohexane is a datum line of 0 degrees).
The electrochemical test and the absorption performance decay test results of the amorphous carbon negative electrode material prepared in the embodiment are shown in table 1.
Comparative example 1
The specific preparation method of this comparative example refers to example 1 except that the operations of steps (2) and (3) are not performed, i.e., the gel polymerization reaction is performed without adding an organic complex and the swelling and etching pore-forming are performed without adding a curing swelling agent.
The electrochemical test and the adsorption performance attenuation test results of the hard carbon negative electrode material prepared in the comparative example are shown in table 1.
Comparative example 2
The specific preparation method of this comparative example was conducted in the same manner as in example 1 except that the operation of step (3), i.e., the gel polymerization reaction was conducted by adding the organic complex compound and the swelling and etching pore-forming was conducted without adding the curing swelling agent.
The electrochemical test and the adsorption performance attenuation test results of the hard carbon negative electrode material prepared in the comparative example are shown in table 1.
Performance test method
The negative electrode materials prepared in each example and comparative example were assembled into a button cell according to the negative electrode material Super-P: CMC of 96.5:1.5:2 as a working electrode and a lithium sheet as a positive electrode, and the first capacity was tested using a blue cell test system. In addition, each will carry outThe negative electrode materials prepared in examples and comparative examples are prepared into a winding soft package battery, and the formulation ratio of the negative electrode coating is that the negative electrode material CMC and SBR (styrene butadiene rubber) are 96.5:1.5:2, LiFePO is adopted4A 18650 battery was assembled using 1mol/L of LiPF6/EC + DMC + EMC (v/v 1:1) electrolyte and Celgard2400 separator as a positive electrode material, CMC: SBR 97.3:1.0:1.7 as a positive electrode material,
charging at 0.1C, discharging at 0.1C, and testing the first reversible capacity and the first coulombic efficiency. And the negative electrode materials of the respective examples and comparative examples were sampled and placed in the air for 30 days, and then the first reversible capacity and the first coulombic efficiency after being placed for 30 days were tested as described above.
And charging at 5C, discharging at 5C, and testing the capacity retention rate after 3000 cycles.
The results of the above tests are shown in Table 1
TABLE 1
Figure BDA0002207336110000181
It can be seen from the above examples and comparative examples that examples 1-6 are prepared by adding curing expanding agent by sol-gel assisted process during preparation, polymerizing at low temperature, sintering at high temperature and etching to obtain a three-dimensional foam type graded-pore amorphous carbon negative electrode material. The amorphous carbon negative electrode materials prepared in the embodiments 1 to 6 show excellent electrochemical performances in the aspects of primary reversible capacity, high-rate long-cycle capacity retention rate and the like, and the surfaces of the materials have a developed ultra-microporous 'rough' structure similar to lotus leaves, so that impurity gases in air are prevented from entering the material structure, and the capacity and the primary effect of the materials are hardly attenuated after the materials are placed in the air.
In example 7, too little addition of the curing expanding agent results in insufficient crosslinking and incomplete curing, and at the same time, the curing expanding agent generates less gas by decomposition, and only a small amount of porous foam structure can be formed.
In example 8, the addition amount of the curing expanding agent is too large, the curing expanding agent is decomposed to generate a large amount of gas in the curing reaction process, a rich macroporous structure is formed, the inner wall is thinned, and a product obtained after the decomposition of the curing expanding agent is further etched at high temperature, so that a part of a porous foam structure is collapsed.
In the comparative example 1, no organic complex is added for carrying out gel polymerization reaction, no curing expanding agent is added for carrying out expansion and etching pore-forming, the surface of the material is not provided with an ultramicropore coating layer, the material is placed in the air for 30 days, water in the air is adsorbed and bonded with microcrystalline gaps of a carbon layer, irreversible active sites are increased, impurity gas is adsorbed, the existing active sites are occupied, and the reversible capacity and the first effect are reduced.
In comparative example 2, no curing expanding agent is added for expansion and etching pore-forming, and the gel cannot be crosslinked and cured to form a foam structure.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (10)

1. The amorphous carbon negative electrode material is characterized by comprising a foam carbon skeleton and carbon particles embedded in the foam carbon skeleton, wherein the surface of the amorphous carbon negative electrode material comprises macropores and ultramicropores.
2. The amorphous carbon negative electrode material of claim 1, wherein the amorphous carbon negative electrode material has a rough structure;
preferably, the amorphous carbon negative electrode material is an integrated self-supporting structure;
preferably, the amorphous carbon anode material has a three-dimensional hierarchical pore structure.
3. The amorphous carbon negative electrode material as claimed in claim 1 or 2, wherein the mass of the carbon particles accounts for 70-98%, preferably 80-95% of the total mass of the amorphous carbon negative electrode material;
preferably, the thickness of the foam type carbon skeleton is 0 to 1.5 μm and does not contain 0;
preferably, the pore size of the macropores is 0.2-3 μm;
preferably, the pore size of the ultramicropores is 0-1.0nm and does not include 0, preferably 0-0.6nm and does not include 0;
preferably, the total pore volume of the amorphous carbon negative electrode material is 0.5-2.0cm3/g;
Preferably, in the amorphous carbon negative electrode material, the pore volume of the ultramicropores accounts for 30-85% of the total pore volume;
preferably, in the amorphous carbon negative electrode material, the pore volume of macropores accounts for 13-70% of the total pore volume;
preferably, the amorphous carbon negative electrode material has a median particle diameter of 8.0 to 40.0 μm, preferably 15.0 to 30.0 μm;
preferably, the carbon particles have a median particle diameter of 0.2 to 3.0 μm, preferably 0.5 to 2.0 μm;
preferably, the specific surface area of the amorphous carbon negative electrode material is 1-50m2A/g, preferably from 1 to 35m2/g;
Preferably, the powder contact angle of the amorphous carbon negative electrode material and water is 40-85 degrees.
4. A method for preparing the amorphous carbon negative electrode material as defined in any one of claims 1 to 3, comprising the steps of:
(1) reacting carbon particles with an organic complex to obtain sol;
(2) adding a curing expanding agent into the sol obtained in the step (1) for reaction to obtain a composite material;
(3) and (3) sintering the composite material obtained in the step (2) to obtain the amorphous carbon negative electrode material.
5. The method according to claim 4, wherein the carbon particles of step (1) have a median particle diameter of 0.2 to 3.0 μm, preferably 0.5 to 2.0 μm;
preferably, the mass ratio of the carbon particles to the organic complex in the step (1) is 1 (0.5-8), and preferably 1 (1-6);
preferably, the method for reacting carbon particles with an organic complex according to step (1) comprises: adding carbon particles into the solution of the organic complex, and heating for reaction to obtain the sol;
preferably, in the solution of the organic complex, the mass fraction of the organic complex is 10-90%, preferably 40-70%;
preferably, the organic complex comprises any one of sucrose, starch, gelatin, phenol-formaldehyde thermoplastic resin, polypyrrole, polyaniline or polyvinyl alcohol or a combination of at least two of them;
preferably, in the solution of the organic complex, the solvent comprises any one of water, ether, alcohol, ketone or tetrahydrofuran or a combination of at least two of the above;
preferably, the reaction temperature of the heating reaction is 40-100 ℃;
preferably, the reaction time of the heating reaction is 1-12 h;
preferably, the heating reaction is accompanied by stirring;
preferably, the heating is performed with an oil bath;
preferably, the stirring rate of the stirring is 10 to 90r/min, preferably 30 to 60 r/min.
6. The method according to claim 4 or 5, wherein the curing expanding agent in step (2) comprises any one or a combination of at least two of sodium bicarbonate, sodium carbonate, sodium oxalate or calcium carbonate;
preferably, the mass ratio of the curing expanding agent to the carbon particles in the step (2) is (0.02-0.8): 1, preferably (0.05-0.5): 1;
preferably, the method for carrying out the reaction of step (2) comprises: heating and curing the expanding agent, mixing, stopping mixing operation, carrying out heating reaction, and drying after reaction to obtain the composite material;
preferably, the mixing method is stirring mixing;
preferably, the stirring speed of the stirring and mixing is 10-90r/min, and preferably 30-60 r/min;
preferably, the mixing time is 0.5-3 h;
preferably, the reaction temperature of the heating reaction is 60-300 ℃;
preferably, the reaction time of the heating reaction is 0.5-10 h;
preferably, the drying method is cooling drying or supercritical drying.
7. The production method according to any one of claims 4 to 6, wherein the sintering in step (3) is performed under a protective atmosphere;
preferably, the protective atmosphere comprises any one of a nitrogen atmosphere, a helium atmosphere, a neon atmosphere, an argon atmosphere or a xenon atmosphere or a combination of at least two of the same;
preferably, the sintering temperature in the step (3) is 600-1500 ℃;
preferably, the sintering time of the step (3) is 0.5-6 h;
preferably, the temperature rise rate of the sintering in the step (3) is 1-30 ℃/min;
preferably, the sintering reactor in the step (3) comprises any one or a combination of at least two of a vacuum furnace, a box furnace, a tube furnace, a roller kiln, a pushed slab kiln, a microwave pyrolysis furnace and an ultraviolet pyrolysis furnace;
preferably, step (3) further comprises: cooling to 15-35 ℃ after sintering;
preferably, step (3) further comprises: purifying a product obtained after sintering;
preferably, the method of purification comprises: stirring and mixing the sintered product with acid, performing suction filtration, washing the obtained solid to be neutral by using water, centrifuging and drying, and demagnetizing and screening the dried product to obtain the amorphous carbon negative electrode material;
preferably, the mass ratio of the product obtained after sintering to the acid is 1:2-1:50, preferably 1:5-1: 20;
preferably, the acid comprises any one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid, or oxalic acid, or a combination of at least two thereof;
preferably, the concentration of the acid is 1-5 mol/L;
preferably, the stirring and mixing time is 0.5-10 h;
preferably, the time of centrifugation is 0.5 to 8 hours, preferably 1.5 to 5 hours;
preferably, the drying is carried out in a vacuum drying oven, a forced air drying oven, a box furnace, a rotary kiln or a double cone dryer;
preferably, the temperature of the drying is 50-200 ℃, preferably 80-150 ℃;
preferably, the drying time is 5-48 h.
8. The method according to any one of claims 4 to 7, wherein the method for preparing the carbon particles of step (1) comprises: carbonizing a carbon precursor in a protective atmosphere to obtain carbon particles;
preferably, the protective atmosphere comprises any one of a nitrogen atmosphere, a helium atmosphere, a neon atmosphere, an argon atmosphere or a xenon atmosphere or a combination of at least two of the same;
preferably, the carbon precursor comprises any one of biomass, resin, pitch or char or a combination of at least two of the foregoing;
preferably, the biomass comprises any one or a combination of at least two of coconut shells, apricot shells, fruit shells or walnut shells;
preferably, the resin comprises any one of furfural resin, phenol resin, melamine formaldehyde resin, epoxy resin, unsaturated polyester, vinyl ester, bismaleimide resin, polyimide resin, polyethylene, polyvinyl chloride, polystyrene, polypropylene or acrylonitrile-styrene-butadiene copolymer or a combination of at least two of them;
preferably, the bitumen comprises any one of coal tar bitumen, shale bitumen or petroleum bitumen or a combination of at least two of the foregoing;
preferably, the coke comprises any one of coal coke, petroleum coke or mesocarbon microbeads or a combination of at least two of the foregoing;
preferably, the temperature of the carbonization is 300-850 ℃;
preferably, the carbonization time is 0.5-8 h;
preferably, the temperature rise rate of the carbonization is 1-10 ℃/min;
preferably, the preparation method of the carbon particle further comprises the following steps: and crushing the product obtained after carbonization.
9. The method for preparing according to any one of claims 4 to 8, characterized in that it comprises the steps of:
(1) heating the carbon precursor to 850 ℃ at the heating rate of 1-10 ℃/min under the protective atmosphere for carbonization, wherein the carbonization time is 0.5-8h, cooling to 15-35 ℃ after carbonization, and crushing the product obtained after carbonization to obtain carbon particles;
(2) adding carbon particles into the solution of the organic complex, heating and reacting under stirring at the reaction temperature of 40-100 ℃ for 1-12h to obtain sol;
the carbon particle has a median particle diameter of 0.5-2.0 μm, the mass ratio of the carbon particle to the organic complex is 1 (1-6), and the mass fraction of the organic complex in the organic complex solution is 40-70%;
(3) adding a curing expanding agent into the sol obtained in the step (2), stirring and mixing for 0.5-3h, stopping stirring, heating and reacting at 60-300 ℃ for 0.5-10h, and drying after reaction to obtain a composite material;
wherein the curing expanding agent is any one or the combination of at least two of sodium bicarbonate, sodium carbonate, sodium oxalate or calcium carbonate, and the mass ratio of the curing expanding agent to the carbon particles is (0.05-0.5) to 1; the drying method is cooling drying or supercritical drying;
(4) heating the composite material obtained in the step (3) to 600-1500 ℃ at the heating rate of 1-15 ℃/min under the protective atmosphere, sintering for 0.5-6h, cooling to 15-35 ℃ after sintering, stirring and mixing the product obtained after sintering and acid with the concentration of 1-5mol/L for 0.5-10h according to the mass ratio of 1:5-1:20, carrying out suction filtration, washing the obtained solid to be neutral by using water, then centrifuging for 1.5-5h, drying for 5-48h at the temperature of 80-150 ℃, and demagnetizing and screening the dried product to obtain the amorphous carbon negative electrode material.
10. Use of the amorphous carbon negative electrode material according to any one of claims 1 to 3, wherein the amorphous carbon negative electrode material is used in a lithium ion battery, a sodium ion battery or a supercapacitor.
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