CN108448096B - High-capacity core-shell type amorphous carbon-based composite material, preparation method thereof and lithium ion battery comprising same - Google Patents

High-capacity core-shell type amorphous carbon-based composite material, preparation method thereof and lithium ion battery comprising same Download PDF

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CN108448096B
CN108448096B CN201810272637.4A CN201810272637A CN108448096B CN 108448096 B CN108448096 B CN 108448096B CN 201810272637 A CN201810272637 A CN 201810272637A CN 108448096 B CN108448096 B CN 108448096B
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carbon
composite material
amorphous carbon
shell
precursor
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CN108448096A (en
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程钢
汪福明
任建国
黄友元
岳敏
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Shenzhen Betray New Material Technology Co.,Ltd.
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention discloses a high-capacity core-shell type amorphous carbon-based composite material, a preparation method thereof and a lithium ion battery containing the same. The core-shell type amorphous carbon-based composite material is a double-shell core-shell structure and comprises an inner core, a first shell and a second shell from inside to outside, wherein the inner core is made of an amorphous carbon material, the first shell is a carbon-silicon coating layer, and the second shell is a carbon coating layer. According to the invention, polyhedral oligomeric silsesquioxane is used as a precursor of the carbon-silicon coating layer, conductive carbon or thermal cracking carbon is further coated to prepare the core-shell type amorphous carbon-based composite material, and the lithium ion battery prepared by using the composite material as a negative electrode active material has excellent comprehensive performance. The specific capacity can reach 553.1mAh/g, the first effect can reach 87.7%, the capacity retention rate can reach 97.3% after 1C circulation at normal temperature for 50 weeks, the 0.5C discharge capacity at minus 30 ℃ can reach more than 71.5% of the 0.5C discharge capacity at room temperature, and the safety performance is good.

Description

High-capacity core-shell type amorphous carbon-based composite material, preparation method thereof and lithium ion battery comprising same
Technical Field
The invention relates to the field of lithium ion battery cathode materials, in particular to a core-shell type amorphous carbon-based composite material, a preparation method thereof and a lithium ion battery comprising the same, and especially relates to a high-capacity core-shell type amorphous carbon-based composite material, a preparation method thereof and a lithium ion battery comprising the same.
Background
Generally, the negative electrode material of the power battery needs to have the characteristics of excellent quick charging performance, higher energy density, lower cost, better safety performance and the like. The amorphous carbon comprises soft carbon and hard carbon, has excellent multiplying power, circulation, low temperature and safety performance, and is one of ideal power battery cathode materials. However, the energy density of amorphous carbon is low, which is a bottleneck to be solved urgently in realizing the commercial application of amorphous carbon.
Currently, there are two effective methods for increasing the energy density of amorphous carbon: firstly, doping modification is carried out on the silicon nitride film by adopting heteroatoms; secondly, with high-capacity metal-based materials (e.g. Si, Sn, Ge, Pb, SiO, SnO, SbSn, Mg)2Si, etc.) are combined. The doping mode can increase the lithium insertion sites of the amorphous carbon, so that the energy density of the amorphous carbon is improved, but the doping material often has voltage lag, so that the temperature rise in the test process of the finished battery is large, and the safety performance of the lithium ion battery is reduced. At the same time, doping can reduce the cycling performance of the material. The problem of low cycle performance of the material is mainly solved when the material is compounded with a high-capacity metal base material, particularly silicon.
There are three main types of silicon-carbon composites: coated, embedded, molecular contact. The first two silicon-carbon composite materials adopt pure silicon powder as a silicon source, and because the silicon powder has low conductivity and large volume expansion rate in the circulating process, the structure collapse and the falling of active substances of pole pieces are easily caused, so that the circulating performance of the materials is poor. The molecular contact type silicon-carbon composite material adopts an organic precursor containing silicon and carbon elements as a precursor, and the molecular nano-silicon in the obtained structure is highly dispersed in the carbon layer, so that the volume expansion of the silicon can be overcome to the greatest extent, the conductivity is increased, and the molecular contact type silicon-carbon composite material is an ideal dispersion system. At present, the patents of molecular contact type silicon-carbon composite materials are less.
Patent CN 103022435B utilizes silsesquioxane (molecular formula H)8Si8O12) The porous silicon-carbon composite material with high capacity and high cycle performance is invented by taking polyacrylonitrile and graphite as raw materials and carrying out the processes of high-temperature pyrolysis, reduction, coating and the like. But H8Si8O12No functional group reacting with the cross-linking agent can not form a rigid skeleton with a carbon source, carbon and silicon oxide are easy to phase separate after pyrolysis, and the size of silicon in the obtained silicon-carbon composite material is far larger than H8Si8O12The silicon has a large volume expansion rate, which affects the cycle performance.
Patent CN103367726A discloses a preparation method of a silicon-carbon composite material: firstly, a silicon dioxide coating layer is formed on the surface of a carbon material by a sol-gel method, and then, the silicon dioxide is partially reduced into a silicon simple substance by adopting metal with strong reducibility. In this structure, the carbon material provides a conductive skeleton of silicon. The method can form a more uniform silicon-containing coating layer on the surface of the carbon-based material, but the volume expansion of silicon is larger, and the carbon simple substance and the silicon-containing coating layer are easy to separate in the lithium intercalation and deintercalation process, so that the silicon loses electric contact and becomes inert silicon. Meanwhile, in the silicon-carbon material, the size of silicon is large, and the pulverization is easy to occur in the process of repeatedly inserting and extracting lithium, so that the capacity attenuation is caused.
Therefore, how to modify amorphous carbon to improve the capacity performance of amorphous carbon on the basis of keeping the excellent multiplying power, cycle and low-temperature performance of amorphous carbon is a technical difficulty for realizing the commercial application of amorphous carbon.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a high-capacity core-shell type amorphous carbon-based composite material, a preparation method thereof and a lithium ion battery comprising the same. The lithium ion battery prepared by using the composite material as a negative electrode material has high capacity, good rate performance, good low-temperature performance and excellent cycle performance.
The high capacity in the high capacity core-shell type amorphous carbon-based composite material refers to the specific capacity of more than 400 mAh/g.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a core-shell type amorphous carbon-based composite material, in particular a high-capacity core-shell type amorphous carbon-based composite material, wherein the composite material is in a core-shell structure with double shell layers, and the double shell layers are a first shell layer and a second shell layer from inside to outside; the core of the composite material is an amorphous carbon material, the first shell layer is a carbon-silicon coating layer, and the second shell layer is a carbon coating layer.
Preferably, the first shell layer is a pyrolytic carbon coating layer embedded with nano silicon.
Preferably, the second shell layer is pyrolytic carbon or a conductive carbon material.
The structural schematic diagram of the core-shell amorphous carbon-based composite material of the invention is shown in fig. 1, wherein 1 represents amorphous carbon, 21 represents nano silicon, 22 represents pyrolytic carbon, 2 represents a carbon-silicon coating layer, and 3 represents a carbon coating layer.
In a preferred embodiment of the composite material of the present invention, the composite material has a median particle diameter of 6 to 50 μm, for example, 6 to 10 μm, 15 to 20 μm, 25 μm, 30 to 33 μm, 36 to 40 μm, 45 μm or 50 μm, preferably 8 to 32 μm, and more preferably 10 to 24 μm.
Preferably, the specific surface area of the composite material is 1m2/g～10m2G, e.g. 1m2/g、2m2/g、3m2/g、5m2/g、7m2/g、8m2/g、9m2G or 10m2G, etc., preferably 1.2m2/g～6m2/g。
Preferably, the powder compaction density of the composite material is 0.7g/cm3～2g/cm3E.g. 0.7g/cm3、1g/cm3、1.2g/cm3、1.5g/cm3、1.8g/cm3Or 2g/cm3Etc., preferably 0.8g/cm3～1.4g/cm3。
In a preferred embodiment of the composite material of the present invention, the median particle diameter of the core is 4 to 28 μm, for example, 4 to 8 μm, 12 μm, 16 μm, 20 μm, 25 μm, 26 μm, 27 μm, or 28 μm, preferably 6 to 18 μm, and more preferably 9 to 15 μm.
Preferably, the amorphous carbon material comprises soft carbon and/or hard carbon.
In a preferred embodiment of the composite material of the present invention, the thickness of the first shell layer is 0 to 3 μm, and does not include 0, for example, 0.1 μm, 0.3 μm, 0.5 μm, 1 μm, 1.2 μm, 1.5 μm, 2 μm, 2.3 μm, 2.5 μm, or 3 μm.
Preferably, the first shell layer is prepared by the following method: polyhedral oligomeric silsesquioxane (POSS) and a cross-linking agent are adopted for surface coating and carbonization, and a carbon-silicon coating layer, namely a first shell layer, is obtained.
In the invention, the polyhedral oligomeric silsesquioxane (POSS) is a chemical general formula (RSiO)1.5)nWherein R represents an organic functional group and n is an even number, typically for example n-8.
Preferably, the R includes any one of alkyl, alkenyl, alkynyl, hydroxyl, aldehyde group, amino, phenyl or carbon branch containing benzene ring or a combination of at least two thereof.
The advantages of the various functional groups described above are:
1) alkyl groups serve as functional groups or carriers for heteroatoms such as N, P.
2) Alkenyl, alkynyl, hydroxyl or aldehyde group: reactive groups may be provided, which react with the crosslinking agent, or with each other.
3) Amino group: and nitrogen doping is provided, and a reactive group which has a crosslinking reaction with a crosslinking agent is provided, so that the structural stability of the carbon-silicon coating layer is improved.
4) Phenyl and carbon-containing branches of the phenyl ring: the provided reactive group and the cross-linking agent have cross-linking reaction, and the pyrolysis carbon residue rate of the group is higher, thereby being beneficial to providing the structural stability of the carbon-silicon coating layer.
Preferably, the polyhedral oligomeric Silsesquioxane (POSS) is any one of polyhedral octaphenyl Silsesquioxane (Ph-POSS) or polyhedral Octaaminophenyl Silsesquioxane (OAPS).
Preferably, the cross-linking agent is a molecule which is used for organic functional groups R of POSS molecules and contains reactive groups, and the reactive groups contained in the cross-linking agent and the organic functional groups R are subjected to cross-linking reaction to form a cross-linked structure.
In a preferred embodiment of the composite material of the present invention, the thickness of the second shell layer is 0 to 2 μm, and does not include 0, for example, 0.1 μm, 0.2 μm, 0.3 μm, 0.4 μm, 0.6 μm, 0.8 μm, 1 μm, 1.1 μm, 1.3 μm, 1.5 μm, 1.7 μm, 1.8 μm, or 2 μm.
Preferably, in the second shell layer, the pyrolytic carbon is a carbon material obtained by pyrolysis of a carbon source.
Preferably, the carbon source is pitch and/or a high molecular compound.
Preferably, the asphalt comprises any one of coal asphalt, petroleum asphalt, natural asphalt or a mixture of at least two of them.
Preferably, the high molecular compound includes any one or a mixture of at least two of epoxy resin, phenolic resin, furfural resin, urea resin, polyvinyl alcohol, polyvinyl chloride, polyethylene glycol, polyethylene oxide, polyvinylidene fluoride, polystyrene, polyvinyl alcohol, polyaniline, acrylic resin, and polyacrylonitrile.
Preferably, in the second shell layer, the conductive carbon material is a carbon material obtained by Chemical Vapor Deposition (CVD) using a gas of an organic carbon source.
Preferably, the organic carbon source is any 1 or combination of at least 2 of hydrocarbons, ketones or aromatic hydrocarbon derivatives with 1-3 rings, preferably 1 or combination of at least 2 of methane, ethylene, acetylene, acetone, benzene, toluene, xylene, styrene or phenol.
In a second aspect, the present invention provides a method for preparing a core-shell amorphous carbon-based composite material according to the first aspect, the method comprising the steps of:
(1) adopting polyhedral oligomeric silsesquioxane and a cross-linking agent to coat the surface of amorphous carbon (named as C1), and then carrying out first carbonization to obtain a coating containing SiO2First amorphous carbon composite precursor (named C1@ SiO) of (ii)2/C2)；
(2) Under the atmosphere of protective gas, reducing agent is adopted to reduce SiO contained in the coating layer2The first amorphous carbon composite precursor is reduced and then subjected to acid treatment to obtain a second amorphous carbon composite precursor (named as C1@ Si/C2), wherein the second amorphous carbon composite precursor comprises an amorphous carbon core and a carbon-silicon coating layer;
(3) coating the second amorphous carbon composite precursor by using a carbon source, and performing second carbonization to obtain a core-shell type amorphous carbon-based composite material (named as C1@ Si/C2@ C3) with the outermost layer of pyrolytic carbon;
alternatively, step (3)' is performed without performing step (3): and (2) carrying out gas phase coating by using gas of an organic carbon source by using a gas phase coating method, and then carrying out second carbonization to obtain the core-shell type amorphous carbon-based composite material (named as C1@ Si/C2@ C3') with the outermost layer being conductive carbon.
As a preferable technical solution of the method of the present invention, the method further includes a step of, after the first carbonization in step (1) is completed, scattering and sieving a product obtained by the first carbonization, wherein the scattering is preferably VC scattering, and the mesh number of a sieve used for sieving is preferably 200 meshes or 325 meshes, and more preferably 325 meshes.
Preferably, the method further comprises the steps of breaking up, sieving and demagnetizing the product obtained by the second carbonization after the second carbonization in the step (3), wherein the breaking up is preferably VC breaking up, and the mesh number of a screen used for sieving is preferably 200 meshes or 325 meshes, and is further preferably 325 meshes.
Preferably, the method further comprises the steps of breaking up, sieving and demagnetizing the product obtained by gas phase coating after the gas phase coating in the step (3)' is completed, wherein the breaking up is preferably VC breaking up, and the mesh number of a screen used for sieving is preferably 200 meshes or 325 meshes, and is further preferably 325 meshes.
Preferably, the amorphous carbon of step (1) comprises soft carbon and/or hard carbon.
Preferably, the soft carbon is any 1 or combination of at least 2 of coke-based soft carbon, MCMB-based soft carbon, or carbon fiber-based soft carbon.
As a preferred embodiment of the method of the present invention, the step (1) of preparing the SiO-containing film comprises2The process of the first amorphous carbon composite precursor of (3) is:
stirring and dissolving polyhedral oligomeric silsesquioxane in a solvent A to obtain a mixed solution, adding amorphous carbon into the mixed solution, and uniformly stirring to obtain a siloxane solution containing amorphous carbon;
(II) dissolving a cross-linking agent in the solvent B to obtain a cross-linking agent solution;
(III) adding the solution of the cross-linking agent into the siloxane solution containing amorphous carbon under the stirring condition, and uniformly stirring to obtain precursor slurry;
(IV) heating the precursor slurry under the condition of stirring to evaporate the solvent to obtain a solid-phase product;
alternatively, step (iv)' is performed without performing step (iv): spray drying the precursor slurry to obtain a solid-phase precursor;
(V) solidifying the solid-phase product, and then carrying out first carbonization under a closed condition to obtain the coating containing SiO2The first amorphous carbon composite precursor of (1).
Preferably, the solvent A in the step (I) is any one or a combination of at least two of tetrahydrofuran, ethanol, N-dimethylformamide, ethyl acetate or carbon disulfide.
Preferably, the solvent B in the step (II) is any one or a combination of at least two of tetrahydrofuran, ethanol, N-dimethylformamide, ethyl acetate or carbon disulfide.
Preferably, the mass ratio of the siloxane dry basis to the amorphous carbon in the siloxane solution containing amorphous carbon in the step (II) is 1:9 to 3:7, such as 1:9, 1:8.5, 1:8, 1:7.5, 1:7, 1:6, 1:5.5, 1:5, 1:4, 1:3, 1:2.5 or 3: 7.
In the present invention, the "dry basis weight of siloxane in the siloxane solution containing amorphous carbon" means: mass of siloxane in siloxane solution containing amorphous carbon.
Preferably, in step (III), the ratio of the dry mass of the solution of the crosslinking agent to the dry mass of the siloxane in the siloxane solution is 1:20 to 1:5, such as 1:20, 1:15, 1:14, 1:12, 1:10, 1:8, 1:7, 1:6, or 1:5.
In the present invention, the "dry mass of the solution of the crosslinking agent" means: mass of the crosslinking agent in the solution of the crosslinking agent.
Preferably, in the step (iv)' the spray drying is performed by using a closed spray dryer, and the frequency of the atomizer is 60Hz to 90Hz, such as 60Hz, 70Hz, 75Hz, 80Hz, 85Hz, or 90 Hz; the rotational speed of the atomizer is 10000 rpm-50000 rpm, such as 10000rpm, 15000rpm, 18000rpm, 20000rpm, 25000rpm, 30000rpm, 35000rpm, 40000rpm, 45000rpm or 50000 rpm; the inlet temperature is 180 ℃ to 450 ℃, such as 180 ℃, 200 ℃, 235 ℃, 280 ℃, 330 ℃, 400 ℃ or 450 ℃ and the like; the outlet temperature is 80 ℃ to 110 ℃, for example 80 ℃, 82 ℃, 85 ℃, 88 ℃, 90 ℃, 95 ℃, 100 ℃ or 110 ℃ and the like.
Preferably, the curing in step (v) is performed in an oven, the temperature of the curing is preferably 80 ℃ to 150 ℃, such as 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 110 ℃, 120 ℃, 125 ℃, 135 ℃, 140 ℃ or 150 ℃ and the like, and the time of the curing is preferably 1h to 36h, such as 2h, 5h, 10h, 12h, 16h, 18h, 21h, 25h, 30h or 36h and the like.
Preferably, the first carbonization in the step (v) is performed by any 1 of a tube furnace, a rotary furnace, a push plate furnace and a roller kiln.
Preferably, the temperature of the first carbonization in step (V) is 400 to 1050 ℃, such as 400 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 800 ℃, 850 ℃, 900 ℃, 925 ℃, 950 ℃, 1000 ℃ or 1050 ℃, and the like, preferably 500 to 800 ℃.
Preferably, the time for the first carbonization in step (v) is 1h to 10h, such as 1h, 3.5h, 5h, 6h, 8h, 9h or 10h, etc.
As a preferable embodiment of the method of the present invention, the pair of layers in step (2) comprises SiO2The process of reducing the first amorphous carbon composite precursor of (a) is: will contain SiO2The first amorphous carbon composite precursor and the reducing agent are mixed, high-temperature treatment is carried out in a closed reactor under the protective gas atmosphere condition, and natural cooling is carried out.
Preferably, the reducing agent is any 1 or combination of at least 2 of potassium, calcium, sodium, magnesium, aluminum, iron, zinc, copper, nickel or titanium.
Preferably, the SiO-containing layer2The mass ratio of the first amorphous carbon composite precursor and the reducing agent (3) is 1 (0.2-0.6), for example, 1:0.2,1:0.3, 1:0.35, 1:0.4, 1:0.5 or 1:0.6, etc.
Preferably, the mixing equipment is a VC mixer, and the mixing method comprises the following steps: will contain SiO2The first amorphous carbon composite precursor and the reducing agent are put into a VC mixer and mixed for not less than 15min, for example, 18min, 20min, 25min, 30min, 40min, 50min, 60min, 75min, 80min, 90min, or 120min, preferably 30 min.
Preferably, the rotational speed of the VC mixer is set to 500r/min to 3000r/min, such as 500r/min, 600r/min, 800r/min, 1000r/min, 1250r/min, 1500r/min, 2000r/min, 2500r/min, 3000r/min, or the like.
Preferably, the closed reactor for high-temperature treatment is any 1 of a tube furnace, a rotary furnace, a push plate furnace or a roller kiln.
Preferably, the protective gas atmosphere is any 1 or a combination of at least 2 of a nitrogen atmosphere, an argon atmosphere, a helium atmosphere, a xenon atmosphere, or a neon atmosphere.
Preferably, the high temperature treatment is performed at a temperature of 500 ℃ to 750 ℃, for example, 500 ℃, 550 ℃, 600 ℃, 625 ℃, 650 ℃, 700 ℃, or 750 ℃.
Preferably, the high temperature treatment time is 1h to 6h, such as 1h, 2h, 3h, 3.5h, 4h, 5h or 6 h.
As a preferred technical scheme of the method, the acid treatment process in the step (2) comprises the following steps: and (3) adding the product reduced in the step (1) into acid, soaking and reacting.
In the present invention, the acid used in the acid treatment should be an acid in an amount sufficient to ensure the reaction to proceed sufficiently.
Preferably, the acid is selected from any 1 or a combination of at least 2 of hydrochloric acid, nitric acid, nitrous acid, sulfuric acid, sulfurous acid, carbonic acid, boric acid, phosphoric acid, perchloric acid, acetic acid or benzoic acid.
Preferably, the method further comprises the steps of washing, filtering and drying the residual product after the reaction after the acid treatment in the step (2).
Preferably, the pH value of the washing solution is 5-8, preferably 7, and the solvent used for washing is water.
As a preferred embodiment of the method of the present invention, in the step (3), the mass percentage of the carbon source is 5 wt% to 20 wt%, for example, 5 wt%, 7 wt%, 8 wt%, 10 wt%, 11 wt%, 13 wt%, 15 wt%, 18 wt%, 20 wt%, or the like, preferably 8 wt% to 13 wt%, based on 100 wt% of the total mass of the carbon source and the second amorphous carbon composite precursor.
Preferably, the coating method is any 1 of a solid phase coating method, a liquid phase coating method or a gas phase coating method.
Preferably, the solid phase coating method is: and adding the second amorphous carbon composite precursor and a carbon source into a VC mixer or a fusion machine for VC mixing or fusion.
Preferably, in the solid phase coating method, the rotation speed of the VC mixer and the fusing machine is independently 500r/min to 3000r/min, such as 500r/min, 700r/min, 1000r/min, 1200r/min, 1500r/min, 1800r/min, 2000r/min, 2300r/min, 2700r/min or 3000 r/min.
Preferably, in the solid phase coating method, the time for mixing or fusing the VC is independently not less than 15min, such as 20min, 30min, 45min, 60min, 100min, 150min, 180min, 220min or 300 min.
Preferably, the liquid phase coating method is: dissolving or dispersing a carbon source in a solvent, uniformly stirring, then adding a second amorphous carbon composite precursor into the obtained mixed solution, uniformly stirring, and heating to evaporate the solvent or spray-drying to obtain a solid-phase product.
Preferably, in the liquid phase coating method, the solvent is any 1 or a combination of at least 2 of tetrahydrofuran, ethanol, isopropanol, carbon disulfide, benzene, toluene or ethyl acetate.
Preferably, in the liquid phase coating method, the spray drying conditions are as follows: the atomizer frequency is 60Hz to 90Hz, such as 60Hz, 70Hz, 75Hz, 80Hz, 85Hz or 90Hz, etc.; the rotational speed of the atomizer is 10000 rpm-50000 rpm, such as 10000rpm, 15000rpm, 18000rpm, 20000rpm, 25000rpm, 30000rpm, 35000rpm, 40000rpm, 45000rpm or 50000 rpm; the inlet temperature of spray drying is 180-450 deg.C, such as 180 deg.C, 200 deg.C, 235 deg.C, 280 deg.C, 330 deg.C, 400 deg.C or 450 deg.C; the outlet temperature is 80 ℃ to 110 ℃, for example 80 ℃, 82 ℃, 85 ℃, 88 ℃, 90 ℃, 95 ℃, 100 ℃ or 110 ℃ and the like.
Preferably, the temperature of the second carbonization in the step (3) is 900 to 1100 ℃, such as 900 ℃, 920 ℃, 950 ℃, 980 ℃, 1000 ℃, 1050 ℃, or 1100 ℃, and the like.
Preferably, the time of the second carbonization in the step (3) is 1h to 8h, such as 1h, 2h, 2.5h, 3h, 4h, 5h, 6h, 6.5h, 7h or 8h, and the like, and preferably 2h to 4 h.
Preferably, the gas phase coating method of step (3)' is: and (3) placing the second amorphous carbon composite precursor in a reaction furnace, introducing protective gas, heating to 600-1200 ℃, introducing gas of an organic carbon source, reacting, and cooling.
In the step (3)' of the invention, if the organic carbon source is gas, the gas is directly introduced; if the organic carbon source is non-gaseous, the organic carbon source is converted into a gaseous state and then introduced.
Preferably, in the vapor phase coating method of step (3)', the organic carbon source is any 1 or a combination of at least 2 of hydrocarbons, ketones, or 1 to 3 ring aromatic hydrocarbon derivatives, preferably any 1 or a combination of at least 2 of methane, ethylene, acetylene, acetone, benzene, toluene, xylene, styrene, or phenol.
Preferably, in the gas phase coating method of step (3)', the reaction furnace is a rotary furnace, and the rotation speed of the rotary furnace is 0.1r/min to 5r/min, such as 0.1r/min, 0.5r/min, 1r/min, 1.5r/min, 2r/min, 3r/min, 3.5r/min, 4r/min or 5 r/min.
Preferably, in the gas phase coating method of step (3)', the flow rate of the organic carbon source gas is 0.1L/min to 2L/min, for example, 0.1L/min, 0.5L/min, 1L/min, 1.2L/min, 1.5L/min, 1.8L/min, 2L/min or the like.
Preferably, in the gas phase coating method of step (3)', the reaction is carried out under an incubation condition for 0.5h to 10h, such as 0.5h, 0.8h, 1h, 2h, 3h, 4.5h, 6h, 7h, 8h or 10 h.
In a third aspect, the present invention provides an anode material, wherein the anode material is the core-shell amorphous carbon-based composite material of the first aspect.
In a fourth aspect, the present invention provides a lithium ion battery comprising the core-shell amorphous carbon-based composite material according to claim 9.
Compared with the prior art, the core-shell type amorphous carbon-based composite material has the advantages that:
(1) the conventional silicon source and carbon source mixture can generate carbon and silicon oxide phase separation after pyrolysis, so that the silicon in the obtained silicon-carbon composite material has a large size and a large volume expansion rate, and the cycle performance of the silicon-carbon composite material is influenced. According to the invention, POSS is used as a silicon source and a carbon source of the carbon-silicon coating layer of the first shell, the size of the silicon simple substance is in a nanometer level, and the silicon simple substance is highly dispersed in pyrolytic carbon of the first shell, so that the composite material belongs to a molecular contact type silicon-based material and has excellent performance. Compared with the traditional silicon-carbon composite material, the core-shell type amorphous carbon-based composite material has the advantages of high specific capacity, good cycle performance and good low-temperature performance.
Secondly, the amorphous carbon is used as the inner core, and the pyrolytic carbon coating layer embedded with the nano silicon is used as the first shell layer to coat the surface of the inner core, so that the amorphous carbon has excellent multiplying power, circulation and low-temperature performance, and high specific capacity (theoretical specific capacity of 4200mAh/g) of silicon, the defect of low energy density is overcome, and the complementary advantages are strong.
And finally, the outermost layer is coated with conductive carbon or pyrolytic carbon, so that direct contact between a silicon-containing part and electrolyte can be avoided, the conductivity of the material is improved, and the influence of silicon volume expansion on the cycle performance of the material is further inhibited.
(2) The specific capacity of the lithium ion battery prepared by using the core-shell amorphous carbon-based composite material as a negative active material can reach 553.1mAh/g, the first effect can reach 87.7%, the capacity retention rate of 50 cycles at normal temperature under 1C can reach 97.3%, the low-temperature performance is excellent, the capacity retention rate of 0.5C-30 ℃/0.5C RT is more than or equal to 71.5%, namely the 0.5C discharge capacity at-30 ℃ is more than 71.5% of the 0.5C discharge capacity at room temperature.
Drawings
Fig. 1 is a schematic structural diagram of a core-shell amorphous carbon-based composite material obtained in the present invention, wherein 1 represents amorphous carbon, 21 represents nano-silicon, 22 represents pyrolytic carbon, 2 represents a carbon-silicon coating layer, and 3 represents a carbon coating layer;
FIG. 2 is a schematic representation of the curing reaction of the oligomeric phenolic resins of the OAPS and Resol types of example 1;
FIG. 3 is an SEM photograph of a core-shell amorphous carbon-based composite material obtained in example 1;
FIGS. 4a and 4b are SEM images of the core-shell type amorphous carbon-based composite material obtained in example 1;
FIG. 5 is a first charge and discharge curve of the coke-based soft carbon and the amorphous carbon-based composite material obtained in example 1;
FIG. 6 is an XRD curve of the coke-based soft carbon and amorphous carbon-based composite material of example 1;
FIG. 7 is a plot of chargeback 1C @50 cycle cycles for the amorphous carbon-based composite obtained in coke-based soft carbon, example 1 and comparative examples 1 and 2;
wherein "coke-like soft carbon" in the figure means: example 1 coke-based soft carbon feedstock used in step S2.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
Batteries were prepared under the same conditions using the amorphous carbon-based composite materials prepared in examples 1 to 5 and comparative examples 1 and 2 as negative electrode materials.
The preparation of the button cell is carried out by adopting a method known in the field: adjusting the negative electrode material, the conductive agent and the binder to a solid content of 50% by mass with distilled water according to a mass ratio of 91:3:6, uniformly mixing, coating on a copper foil current collector, and drying in vacuum to obtain a negative electrode plate; 1mol/L LiPF with lithium plate as counter electrode6The electrolyte is/EC + DMC + EMC (v/v is 1:1:1), the diaphragm is Celgrad2400, and the outer shell adopts a 2016 button cell outer shell.
The preparation method of the specific cylindrical battery comprises the following steps: dispersing the negative electrode material, the conductive agent and the binder in a solvent according to the mass percentage of 94:1:5, uniformly mixing, controlling the solid content to be 50%, coating the mixture on a copper foil current collector, and drying in vacuum to obtain a negative electrode piece; then, an NCM positive pole piece prepared by a traditional mature process, 1mol/L LiPF6/EC + DMC + EMC (v/v is 1:1:1) electrolyte, a Celgard2400 diaphragm and an outer shell are assembled into the 18650 cylindrical single-cell battery by adopting a conventional production process.
By adopting a power-off method, the specific capacity and the first efficiency test conditions of the amorphous carbon-based composite materials obtained in the examples 1-5 and the comparative examples 1 and 2 are as follows: the test is carried out on a LAND battery test system of Wuhanjinnuo electronic Limited company, wherein 0.1C is discharged, the cut-off voltage is 1mV, then 0.1C is charged, the cut-off voltage is 1.5V, and the test result is shown in Table 1.
By adopting a power-off method, the test conditions of the 1C @ 50-week cycle performance of the amorphous carbon-based composite materials obtained in the examples 1-5 and the comparative examples 1 and 2 are as follows: the test is carried out on a LAND battery test system of Wuhanjinnuo electronic Limited company, the charging and discharging are sequentially activated for 2 weeks at the multiplying power of 0.1C, 0.2C and 0.5C, then the charging and discharging multiplying power is increased to 1C, and the cycle performance test is carried out under the normal temperature condition, and the result is shown in table 1.
The specific surface areas of the amorphous carbon-based composite materials prepared in examples 1 to 5 and comparative examples 1 and 2 were measured, and the results are shown in table 1.
The coke-based soft carbon and amorphous carbon-based composite material of example 1 was tested for low-temperature performance under 18650 cylindrical battery test conditions, and was tested on a LAND battery test system of Ghanjinuo electronics, Inc., charged at room temperature at 0.5C, allowed to stand at low temperature for 4 hours, and then discharged at 0.5C at different low temperatures (25 deg.C, -20 deg.C, -30 deg.C, and 60 deg.C), with the charging and discharging voltages limited to 2.0V-4.2V, and the test results are shown in Table 2.
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
Example 1
S1: synthesis of the crosslinking agent (solution of oligomeric phenol-formaldehyde resin of the Resol type): phenol was melted with hot water and 48.8g was placed in a three-necked flask and 10.4g of aqueous NaOH (20 wt%) was slowly added dropwise with magnetic stirring. After stirring for 10min, 84g of formaldehyde solution (37 wt%) were added dropwise at 50 ℃ or below. After the dropwise addition, the flask was immersedReflux in a 72 ℃ water bath for 1 h. Cooled to room temperature and the pH adjusted to 7 with 0.6M HCl. Removing water from the obtained neutral solution by rotary evaporation at 45 deg.C to obtain viscous phenolic resin, adding 320g THF, stirring to dissolve the resin, and adding small amount of anhydrous Na2SO4Drying and filtering at normal pressure to obtain the tetrahydrofuran THF solution of the oligomeric phenolic resin with the concentration of 20 wt%.
S2: 88.2g of cage-type Octahedral Amine Phenylsilsesquioxane (OAPS) was dissolved in 2L of tetrahydrofuran, and stirred at room temperature for 30 min. Adding 500g of coke soft carbon into the tetrahydrofuran solution of OAPS under the stirring condition, and stirring for 30 min; adding 44g of 20 wt% THF solution of oligomeric phenolic resin into OAPS/tetrahydrofuran solution containing coke soft carbon under stirring, and stirring for 5 min;
spray drying (atomizer frequency 90Hz, atomizer speed 15000rpm, inlet temperature 300 deg.C, outlet temperature 100 deg.C), scattering the obtained material, and transferring into a forced air oven to cure at 100 deg.C for 24 h. Transferring the cured material to a box furnace, and sintering at 600 ℃ for 4h under the protection of nitrogen, wherein the heating rate is 3 ℃/min. Dispersing the material VC, and screening with 325 meshes to obtain the material containing SiO2First amorphous carbon composite precursor (C1@ SiO)2/C2)。
S3: the obtained product of S2 contains SiO2First amorphous carbon composite precursor (C1@ SiO)2/C2) and magnesium powder are put into a VC mixer according to the mass ratio of 1:0.4, VC mixing is carried out for 15min, the mixture is transferred into a closed container, and the temperature is raised to 700 ℃ under the protection of Ar gas for high-temperature treatment for 3 h. After cooling, the product was transferred to a container, 2L of 3mol/L hydrochloric acid was added, and stirred for 2 hours. After suction filtration, washing with water until the pH value is close to 7, and transferring to a 100 ℃ oven for drying to obtain a second amorphous carbon composite precursor (C1@ Si/C2).
S4: and (3) putting the second amorphous carbon composite precursor (C1@ Si/C2) obtained in the step (S3) into a CVD rotary furnace, and carrying out CVD coating at 800 ℃ for 5h by taking nitrogen as a carrier gas and a protective gas and acetylene as a coating carbon source. After cooling to room temperature, the obtained material was transferred to a tube furnace and sintered at 950 ℃ for 3h under nitrogen protection with a heating rate of 3 ℃/min. Sieving with 325 mesh sieve to obtain the core-shell type amorphous carbon-based composite material (C1@ Si/C2@ C3).
FIG. 2 is a schematic representation of the curing reaction of the OAPS and Resol type oligomeric phenolic resins of example 1.
Fig. 3 is an SEM image and a sectional SEM of the core-shell type amorphous carbon-based composite material obtained in example 1, and it can be seen from the images that the particles of the amorphous carbon-based composite material are uniform and no cross-linking between the particles is evident.
Fig. 4 is a cross-sectional SEM image of the core-shell type amorphous carbon-based composite material obtained in example 1, which shows that the amorphous carbon-based composite material includes, from inside to outside, an inner core, a first shell layer and a second shell layer, wherein the inner core is an amorphous carbon material, the first shell layer is a carbon-silicon coating layer, and the second shell layer is a carbon coating layer.
Fig. 5 is a first charge-discharge curve of the coke soft carbon and core-shell amorphous carbon-based composite material in example 1, and it can be seen from the graph that the specific capacity of the core-shell amorphous carbon-based composite material is 210mAh/g higher than that of the coke soft carbon, which indicates that the capacity performance of the amorphous carbon can be significantly improved by the carbon-silicon composite method.
Fig. 6 is an XRD curve of the pyro soft carbon and amorphous carbon-based composite material of example 1, from which it can be seen that the D002 diffraction peak of the pyro soft carbon of example 1 is strong, whereas the D002 diffraction peak of the core-shell amorphous carbon-based composite material obtained in example 1 is weak, and the latter has a diffraction peak corresponding to silicon element at 2 θ of 28.52 °.
Fig. 7 is a chargeback 1C @ 50-cycle curve of the coke-based soft carbon, the amorphous carbon-based composite materials obtained in example 1 and comparative examples 1 and 2, and it can be seen from the figure that the 1C normal temperature cycle performance: the coke-like soft carbon (example 1) ≈ core-shell amorphous carbon-based composite material (example 1) > carbon-silicon composite material (comparative example 2) > carbon-silicon composite material (comparative example 1), thus showing: polyhedral oligomeric silsesquioxane (POSS) is used as a silicon source, and the carbon-silicon composite material prepared by using nano-silicon as the silicon source has the cycle performance because the silicon particles in the carbon-silicon composite material prepared by using the polyhedral oligomeric silsesquioxane (POSS) are smaller in size and more uniform in dispersion.
Example 2
S1: the crosslinker was prepared in the same manner as in example 1 to give a 20 wt% strength solution of the oligomeric phenol-formaldehyde resin in THF.
S2: 88.2g of cage-type Octahedral Amine Phenylsilsesquioxane (OAPS) was dissolved in 2L of tetrahydrofuran, and stirred at room temperature for 40 min. Adding 500g of MCMB soft carbon into the tetrahydrofuran solution of OAPS under the stirring condition, and stirring for 25 min;
adding 44g of 20 wt% THF solution of oligomeric phenolic resin into the solution of tetrahydrofuran containing MCMB soft carbon under stirring, and stirring for 20 min;
spray drying (atomizer frequency 60Hz, atomizer rotation speed 40000rpm, inlet temperature 300 deg.C, outlet temperature 110 deg.C), breaking the obtained material, and transferring into a forced air oven to cure at 135 deg.C for 4 h. Transferring the cured material to a box furnace, and sintering for 2h at 500 ℃ under the protection of nitrogen, wherein the heating rate is 4 ℃/min. Dispersing the material VC, and screening with 325 meshes to obtain the material containing SiO2First amorphous carbon composite precursor (C1@ SiO)2/C2)。
S3: the obtained product of S2 contains SiO2First amorphous carbon composite precursor (C1@ SiO)2/C2) and aluminum powder are put into a VC mixer according to the mass ratio of 1:0.3, VC mixing is carried out for 30min, the mixture is transferred into a closed container, and the temperature is raised to 600 ℃ under the protection of Ar gas for high-temperature treatment for 6 h. After cooling, the product was transferred to a beaker, 3L of 3mol/L sulfuric acid was added and stirred for 1.5 h. And after suction filtration, washing with water until the pH value is close to 7, transferring to an oven at 80 ℃ and drying to obtain a second amorphous carbon composite precursor (C1@ Si/C2), wherein the second amorphous carbon composite precursor comprises an MCMB soft carbon core and a carbon-silicon coating layer.
S4: and (3) putting the second amorphous carbon composite precursor (C1@ Si/C2) obtained in the step (S3) into a CVD rotary furnace, and carrying out CVD coating at 850 ℃ for 5 hours by using nitrogen as a carrier gas and a protective gas and acetylene as a coating carbon source (the flow rate is 2L/min). After cooling to room temperature, the obtained material was transferred to a tube furnace and sintered at 950 ℃ for 3h under nitrogen protection with a heating rate of 3 ℃/min. Sieving with 325 mesh sieve to obtain the core-shell type amorphous carbon-based composite material (C1@ Si/C2@ C3).
Example 3
S1: the crosslinker was prepared in the same manner as in example 1 to give a 20 wt% strength solution of the oligomeric phenol-formaldehyde resin in THF.
S2: 88.2g of cage-type Octahedral Amine Phenylsilsesquioxane (OAPS) was dissolved in 2L of tetrahydrofuran, and stirred at room temperature for 45 min. Adding 500g of carbon fiber soft carbon into the tetrahydrofuran solution of OAPS under the stirring condition, and stirring for 30 min;
under the stirring condition, 66g of a THF solution of 20 wt% of oligomeric phenolic resin is added into a tetrahydrofuran solution containing carbon fiber soft carbon, and the mixture is stirred for 20 min;
spray drying (atomizer frequency 90Hz, atomizer speed 15000rpm, inlet temperature 350 deg.C, outlet temperature 100 deg.C), scattering the obtained material, and transferring into a forced air oven to cure at 120 deg.C for 12 h. And transferring the cured material to a tubular furnace, and sintering at 500 ℃ for 10h under the protection of nitrogen, wherein the heating rate is 5 ℃/min. Dispersing the material VC, and screening with 325 meshes to obtain the material containing SiO2First amorphous carbon composite precursor (C1@ SiO)2/C2)。
S3: the obtained product of S2 contains SiO2First amorphous carbon composite precursor (C1@ SiO)2/C2) and calcium powder according to the mass ratio of 1:0.6, putting into a VC mixer, mixing for 60min, transferring the mixture into a closed container, and heating to 750 ℃ under the protection of He gas for high-temperature treatment for 2.5 h. After cooling, the product was transferred to a beaker, 2.5L of 1.5mol/L hydrochloric acid was added and stirred for 3 h. And after suction filtration, washing with water until the pH value is close to 7, transferring to a 90 ℃ oven, and drying to obtain a second amorphous carbon composite precursor (C1@ Si/C2), wherein the second amorphous carbon composite precursor comprises a carbon fiber soft carbon core and a carbon-silicon coating layer.
S4: the second amorphous carbon composite precursor (C1@ Si/C2) obtained in S3 was put into a CVD rotary furnace, and CVD coating was performed at 850 ℃ for 6 hours using nitrogen as a carrier gas and a protective gas and acetone as a coating carbon source (flow rate 0.8L/min). After cooling to room temperature, the obtained material is transferred into a tube furnace and sintered for 2h at 950 ℃ under the protection of nitrogen, and the heating rate is 3 ℃/min. Sieving with 325 mesh sieve to obtain the core-shell type amorphous carbon-based composite material (C1@ Si/C2@ C3).
Example 4
S1: the crosslinker was prepared in the same manner as in example 1 to give a 20 wt% strength solution of the oligomeric phenol-formaldehyde resin in THF.
S2: 88.2g of cage-type Octahedral Amine Phenylsilsesquioxane (OAPS) was dissolved in 2L of tetrahydrofuran, and stirred at room temperature for 45 min. Adding 500g of plant hard carbon into tetrahydrofuran solution of OAPS under stirring, and stirring for 30 min;
adding 44g of 20 wt% THF solution of oligomeric phenolic resin into tetrahydrofuran solution containing plant hard carbon under stirring, and stirring for 20 min;
heating and evaporating the solvent to dryness under the condition of stirring to obtain a material, scattering the obtained material, and transferring the scattered material into a blast oven to be cured for 2 hours at the temperature of 150 ℃. And transferring the cured material to a tubular furnace, and sintering for 6h at 650 ℃ under the protection of nitrogen, wherein the heating rate is 3 ℃/min. Dispersing the material VC, and screening with 325 meshes to obtain the material containing SiO2First amorphous carbon composite precursor (C1@ SiO)2/C2)。
S3: the obtained product of S2 contains SiO2First amorphous carbon composite precursor (C1@ SiO)2/C2) and magnesium powder are put into a VC mixer according to the mass ratio of 1:0.5, VC mixing is carried out for 100min, the mixture is transferred into a closed container, and the temperature is raised to 725 ℃ under the protection of Ar gas for high-temperature treatment for 5 h. After cooling, the product was transferred to a beaker, 2.5L of 3mol/L nitric acid was added and stirred for 4 h. And after suction filtration, washing with water until the pH value is close to 7, transferring to a 95 ℃ oven, and drying to obtain a second amorphous carbon composite precursor (C1@ Si/C2), wherein the second amorphous carbon composite precursor comprises a plant hard carbon core and a carbon-silicon coating layer.
S4: and (2) putting the second amorphous carbon composite precursor (C1@ Si/C2) obtained in the step S3 and asphalt into a fusion machine according to a certain mass ratio (C1@ Si/C2: 9:1), carrying out fusion treatment for 30min at the fusion machine rotating speed of 1500r/min, transferring the obtained material into a tube furnace, and sintering for 3h at 950 ℃ under the protection of nitrogen at the heating rate of 5 ℃/min. Sieving with 325 mesh sieve to obtain the core-shell type amorphous carbon-based composite material (C1@ Si/C2@ C3).
Example 5
S1: the crosslinker was prepared in the same manner as in example 1 to give a 20 wt% strength solution of the oligomeric phenol-formaldehyde resin in THF.
S2: 214.3g of cage-type Octahedral Amine Phenylsilsesquioxane (OAPS) was dissolved in 2L of tetrahydrofuran, and stirred at room temperature for 60 min. Adding 500g of pitch hard carbon into tetrahydrofuran solution of OAPS under the condition of stirring, and stirring for 35 min;
under the stirring condition, 66g of a 20 wt% THF solution of the oligomeric phenolic resin is added into a tetrahydrofuran solution containing the pitch hard carbon, and the mixture is stirred for 25 min;
heating and evaporating the solvent to dryness under the condition of stirring to obtain a material, scattering the obtained material, and transferring the scattered material into a blast oven to be cured for 5 hours at the temperature of 140 ℃. Transferring the cured material to a tubular furnace, and sintering at 600 ℃ for 3h under the protection of nitrogen, wherein the heating rate is 3 ℃/min. Dispersing the material VC, and sieving with 200 meshes to obtain the material VC containing SiO2First amorphous carbon composite precursor (C1@ SiO)2/C2)。
S3: the obtained product of S2 contains SiO2First amorphous carbon composite precursor (C1@ SiO)2/C2) and zinc powder are put into a VC mixer according to the mass ratio of 1:0.4, VC is mixed for 100min, the mixture is transferred into a closed container and is added into a container in N2Raising the temperature to 675 ℃ under the protection of gas and treating for 3.5 h. After cooling, the product was transferred to a vessel, 2.5L of 3mol/L nitric acid was added, and stirred for 4 h. And after suction filtration, washing with water until the pH value is close to 7, transferring to a drying oven at 100 ℃ and drying to obtain a second amorphous carbon composite precursor (C1@ Si/C2), wherein the second amorphous carbon composite precursor comprises a pitch hard carbon core and a carbon-silicon coating layer.
S4: and (2) putting the second amorphous carbon composite precursor (C1@ Si/C2) obtained in the step S3 and asphalt into a VC mixer according to a certain mass ratio (C1@ Si/C2: asphalt is 9:1), mixing at the rotating speed of 3000r/min for 65min, transferring the obtained material into a tube furnace, and sintering at 950 ℃ for 3h under the protection of nitrogen at the heating rate of 5 ℃/min. Sieving with 325 mesh sieve to obtain the core-shell type amorphous carbon-based composite material (C1@ Si/C2@ C3).
Comparative example 1
The amorphous carbon-based composite material (C1@ Si/C2@ C3) was prepared under the same conditions as in example 1, except that the soft coke-based carbon was not added in step S2.
Comparative example 2
Adding nano silicon powder with the median particle size of 100-200 mu m and a dispersing agent into isopropanol, and performing high-energy ball milling for 24 hours at the rotating speed of 300r/min to obtain silicon slurry with the solid content (the mass of the nano silicon divided by the total mass of the silicon slurry) of about 10 wt%. Adding silicon slurry containing 37.6g of nano-silicon into 2L of THF, adding 500g of coke soft carbon and 52.3g of asphalt into the solution, uniformly stirring, spray-drying (the frequency of an atomizer is 90Hz, the rotating speed of the atomizer is 15000rpm, the inlet temperature is 300 ℃, the outlet temperature is 100 ℃), scattering the obtained material, transferring the scattered material into a box furnace, sintering at 500 ℃ for 3h under the protection of nitrogen, and heating at the rate of 3 ℃/min. And (3) scattering the material VC, and screening by a 325-mesh sieve to obtain an amorphous carbon composite precursor (C1@ Si/C2).
The obtained C1@ Si/C2 was subjected to CVD acetylene coating and carbonization sintering (950 ℃, 3h) according to the method and parameters of S4 in example 1, and sieved with a 325-mesh screen, so as to obtain a core-shell type amorphous carbon-based composite material (C1@ Si/C2@ C3).
TABLE 1 indexes of physical Properties of amorphous carbon-based composite materials of examples 1 to 5 and comparative examples 1 to 2
Figure BDA0001612925300000211
TABLE 2 EXAMPLE 1 Low-temperature Performance of coke-based Soft carbon and amorphous carbon-based composite Material
Figure BDA0001612925300000212
Figure BDA0001612925300000221
As can be seen from Table 1, the specific capacity of the core-shell amorphous carbon-based composite materials obtained in examples 1-5 and comparative examples 1 and 2 is greater than 400mAh/g, the first efficiency is greater than 86.5%, and the core-shell amorphous carbon-based composite materials show higher capacity.
By comparing examples 1-5 with comparative examples 1-2, the cyclic performance is poor due to the fact that coke soft carbon is not added as a core in comparative example 1, the silicon content is high, the expansion of the material in the charging and discharging process is large, and the prepared silicon-carbon composite is irregular in shape and difficult to completely coat, so that the silicon-containing part of the material is in direct contact with electrolyte, and the cyclic performance is further reduced.
The silicon source adopted in the comparative example 2 is nano silicon powder, the median particle size of the silicon powder is 50-300 nm, the particle size is larger, the expansion rate is high, and the cycle performance is poor. And the oligomeric silsesquioxane adopted in the embodiment is a silicon source, and the particle size of silicon obtained by the silicon source is smaller than 1nm, so that the expansion rate of the obtained silicon-carbon composite is smaller than that of the silicon-carbon composite in a comparative example 2, and the cycle performance is better.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. 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 (85)

1. The core-shell type amorphous carbon-based composite material is characterized in that the composite material is of a core-shell structure with double shell layers, wherein the double shell layers are a first shell layer and a second shell layer from inside to outside;
the inner core of the composite material is made of amorphous carbon material, the first shell layer is a pyrolytic carbon coating layer embedded with nano silicon, and the second shell layer is a carbon coating layer;
the first shell layer is prepared by the following method: adopting polyhedral oligomeric silsesquioxane (POSS) and a cross-linking agent to perform surface coating and carbonization on the amorphous carbon material, adding a reducing agent to perform reduction, and performing acid treatment to obtain a carbon-silicon coating layer, namely the first shell layer;
said facetsPolyhedral oligomeric silsesquioxane POSS is a compound with a chemical general formula of (RSiO)1.5)nWherein R represents a functional group, n is an even number, and the R comprises any one or the combination of at least two of alkyl, alkenyl, alkynyl, hydroxyl, aldehyde group, amino, phenyl or a carbon branched chain containing a benzene ring;
the reactive group contained in the cross-linking agent and the functional group R are subjected to cross-linking reaction to form a cross-linked structure.
2. The composite material of claim 1, wherein the composite material has a median particle size of 6 μ ι η to 50 μ ι η.
3. The composite material of claim 2, wherein the composite material has a median particle size of 8 μm to 32 μm.
4. The composite material according to claim 3, wherein the median particle size of the composite material is from 10 μm to 24 μm.
5. The composite material according to claim 1, characterized in that the specific surface area of the composite material is 1m2/g～10m2/g。
6. Composite material according to claim 5, characterized in that the specific surface area of the composite material is 1.2m2/g～6m2/g。
7. The composite material of claim 1, wherein the composite material has a powder compaction density of 0.7g/cm3～2g/cm3。
8. The composite material of claim 7, wherein the composite material has a powder compaction density of 0.8g/cm3～1.4g/cm3。
9. The composite material of claim 1, wherein the median particle size of the inner core is from 4 μm to 28 μm.
10. The composite material of claim 9, wherein the median particle size of the inner core is from 6 μm to 18 μm.
11. The composite material of claim 10, wherein the median particle size of the inner core is from 9 μ ι η to 15 μ ι η.
12. The composite material according to claim 1, wherein the amorphous carbon material comprises soft carbon and/or hard carbon.
13. The composite material as claimed in claim 1, wherein the first shell layer has a thickness of 0 to 3 μm and does not include 0.
14. The composite material of claim 1, wherein polyhedral oligomeric silsesquioxane (POSS) is any one of polyhedral octaphenyl silsesquioxane (Ph-POSS) or polyhedral octaamine phenyl silsesquioxane (OAPS).
15. The composite material as claimed in claim 1, wherein the second shell layer has a thickness of 0 to 2 μm and does not include 0.
16. The composite material of claim 1, wherein the second shell layer is a pyrolytic carbon or conductive carbon material.
17. The composite material of claim 1, wherein in the second shell layer, the pyrolytic carbon is a carbon material obtained by pyrolysis of a carbon source.
18. Composite according to claim 17, characterized in that the carbon source is a pitch and/or a polymeric compound.
19. The composite of claim 18, wherein the pitch comprises a mixture of either or both of coal pitch and petroleum pitch.
20. The composite material of claim 18, wherein the polymer compound comprises any one or a mixture of at least two of epoxy resin, phenolic resin, furfural resin, urea resin, polyvinyl alcohol, polyvinyl chloride, polyethylene glycol, polyethylene oxide, polyvinylidene fluoride, polystyrene, polyaniline, acrylic resin, or polyacrylonitrile.
21. The composite material of claim 16, wherein the conductive carbon material in the second shell layer is a carbon material obtained by Chemical Vapor Deposition (CVD) using a gas of an organic carbon source.
22. The composite material of claim 21, wherein the organic carbon source is any 1 or a combination of at least 2 of hydrocarbons, ketones, or aromatic hydrocarbon derivatives with 1-3 rings.
23. The composite material of claim 22, wherein the organic carbon source is 1 or a combination of at least 2 of methane, ethylene, acetylene, acetone, benzene, toluene, xylene, styrene, or phenol.
24. The method of any one of claims 1-23, wherein the method comprises the steps of:
(1) adopting polyhedral oligomeric silsesquioxane (POSS) and a cross-linking agent to coat the surface of amorphous carbon, and then carrying out first carbonization to obtain a coating containing SiO2The first amorphous carbon composite precursor of (a);
(2) under the atmosphere of protective gas, reducing agent is adopted to reduce SiO contained in the coating layer2First amorphous carbon of (2)Reducing the composite precursor, and then carrying out acid treatment to obtain a second amorphous carbon composite precursor, wherein the second amorphous carbon composite precursor comprises an amorphous carbon core and a carbon-silicon coating layer;
(3) coating the second amorphous carbon composite precursor by using a carbon source, and performing second carbonization to obtain a core-shell type amorphous carbon-based composite material with the outermost layer being pyrolytic carbon;
alternatively, step (3)' is performed without performing step (3): and (3) carrying out gas phase coating by using gas of an organic carbon source by using a gas phase coating method, and then carrying out second carbonization to obtain the core-shell type amorphous carbon-based composite material with the outermost layer being conductive carbon.
25. The method according to claim 24, further comprising the step of, after the first carbonization in step (1) is completed, scattering and sieving the product obtained by the first carbonization.
26. The method of claim 25, wherein the break up is VC break up.
27. The method of claim 25, wherein the screen mesh size used for said screening is 200 mesh or 325 mesh.
28. The method of claim 27 wherein said screen uses a mesh size of 325 mesh.
29. The method according to claim 24, further comprising the steps of, after the second carbonization in step (3), scattering, sieving and demagnetizing the product obtained by the second carbonization.
30. The method of claim 29, wherein the break up is VC break up.
31. The method of claim 29, wherein the screen mesh size used for said screening is 200 mesh or 325 mesh.
32. The method of claim 31 wherein said screen uses a mesh size of 325 mesh.
33. The method according to claim 24, further comprising the step of, after the gas phase coating of step (3)' is completed, scattering, sieving and demagnetizing the product obtained by the gas phase coating.
34. The method of claim 33, wherein the break up is VC break up.
35. The method of claim 33, wherein the screen mesh size used for said screening is 200 mesh or 325 mesh.
36. The method of claim 35 wherein said screen uses a mesh size of 325 mesh.
37. The method according to claim 24, wherein the amorphous carbon of step (1) comprises soft carbon and/or hard carbon.
38. The method of claim 37, wherein the soft carbon is 1 or a combination of at least 2 of coke-based soft carbon, MCMB-based soft carbon, carbon fiber-based soft carbon.
39. The method of claim 37, wherein the hard carbon is any 1 or a combination of at least 2 of a resin-based hard carbon, a pitch-based hard carbon, or a plant-based hard carbon.
40. The method of claim 24, wherein step (1) produces a composition comprising SiO2The process of the first amorphous carbon composite precursor of (3) is:
stirring and dissolving polyhedral oligomeric silsesquioxane (POSS) in a solvent A to obtain a mixed solution, adding amorphous carbon into the mixed solution, and uniformly stirring to obtain a siloxane solution containing amorphous carbon;
(II) dissolving a cross-linking agent in the solvent B to obtain a cross-linking agent solution;
(III) adding the solution of the cross-linking agent into the siloxane solution containing amorphous carbon under the stirring condition, and uniformly stirring to obtain precursor slurry;
(IV) heating the precursor slurry under the condition of stirring to evaporate the solvent to obtain a solid-phase product;
alternatively, step (iv)' is performed without performing step (iv): spray drying the precursor slurry to obtain a solid-phase precursor;
(V) solidifying the solid-phase product, and then carrying out first carbonization under a closed condition to obtain the coating containing SiO2The first amorphous carbon composite precursor of (1).
41. The method according to claim 40, wherein the solvent A in step (I) is one or a combination of at least two of tetrahydrofuran, ethanol, N-dimethylformamide, ethyl acetate and carbon disulfide.
42. The method according to claim 40, wherein the solvent B in step (II) is one or a combination of at least two of tetrahydrofuran, ethanol, N-dimethylformamide, ethyl acetate or carbon disulfide.
43. The method as claimed in claim 40, wherein the ratio of the dry mass of siloxane to the mass of amorphous carbon in the siloxane solution containing amorphous carbon in step (I) is 1:9 to 3: 7.
44. The method of claim 40, wherein in step (III), the ratio of the dry mass of the solution of the crosslinking agent to the dry mass of the siloxane in the siloxane solution is from 1:20 to 1:5.
45. The method according to claim 40, wherein the spray drying in step (IV)' is carried out using a closed spray dryer with an atomizer frequency of 60Hz to 90Hz, an atomizer rotation speed of 10000rpm to 50000rpm, an inlet temperature of 180 ℃ to 450 ℃ and an outlet temperature of 80 ℃ to 110 ℃.
46. The method of claim 40, wherein the curing of step (V) is performed in an oven.
47. The method as claimed in claim 40, wherein the curing temperature is 80 ℃ to 150 ℃ and the curing time is 1h to 36 h.
48. The method according to claim 40, wherein the first carbonization in the step (V) is performed by using 1 kind of apparatus selected from the group consisting of a tube furnace, a rotary furnace, a pusher furnace, and a roller kiln.
49. The method according to claim 40, wherein the temperature of the first carbonization in step (V) is 400-1050 ℃.
50. The method according to claim 49, wherein the temperature of the first carbonization in step (V) is 500-800 ℃.
51. The method of claim 40, wherein the first carbonization time in step (V) is 1-10 h.
52. The method of claim 40, wherein the pair of step (2) comprises SiO2The process of reducing the first amorphous carbon composite precursor of (a) is: will contain SiO2The first amorphous carbon composite precursor is mixed with a reducing agent, high-temperature treatment is carried out in a closed reactor under the protective gas atmosphere condition, and natural cooling is carried outBut instead.
53. The method of claim 52, wherein the reducing agent is any 1 or combination of at least 2 of potassium, calcium, sodium, magnesium, aluminum, iron, zinc, copper, nickel, or titanium.
54. The method of claim 52, wherein the SiO-containing layer2The mass ratio of the first amorphous carbon composite precursor to the reducing agent of (1) is (0.2-0.6).
55. The method as claimed in claim 52, wherein the mixing is carried out using a VC mixer by: will contain SiO2The first amorphous carbon composite precursor and the reducing agent are put into a VC mixer and mixed for not less than 15 min.
56. The method of claim 55, wherein the mixing time is 30 min.
57. A method as claimed in claim 55, wherein the speed of rotation of the VC mixer is set to between 500 and 3000 r/min.
58. The method of claim 52, wherein the closed reactor for high temperature treatment is any 1 of a tube furnace, a rotary furnace, a pusher furnace or a roller kiln.
59. The method of claim 52, wherein the protective gas atmosphere is any 1 or a combination of at least 2 of a nitrogen atmosphere, an argon atmosphere, a helium atmosphere, a xenon atmosphere, or a neon atmosphere.
60. The method as claimed in claim 52, wherein the temperature of the high-temperature treatment is 500-750 ℃, and the time of the high-temperature treatment is 1-6 h.
61. The method of claim 24, wherein the acid treatment in step (2) is performed by: and adding the reduced product into acid, soaking and reacting.
62. The method of claim 61, wherein the acid is selected from any 1 or a combination of at least 2 of hydrochloric acid, nitric acid, nitrous acid, sulfuric acid, sulfurous acid, carbonic acid, boric acid, phosphoric acid, perchloric acid, acetic acid, or benzoic acid.
63. The method according to claim 24, further comprising the steps of washing, suction-filtering and drying the product remaining after the reaction after the acid treatment in step (2).
64. The method as claimed in claim 63, wherein the washing is carried out to a pH of 5 to 8, and the solvent used for the washing is water.
65. The method of claim 64, wherein the washing is to a pH of 7.
66. The method according to claim 24, wherein in the step (3), the mass percentage of the carbon source is 5 wt% to 20 wt% based on 100 wt% of the total mass of the carbon source and the second amorphous carbon composite precursor.
67. The method according to claim 66, wherein in the step (3), the mass percentage of the carbon source is 8 wt% to 13 wt% based on 100 wt% of the total mass of the carbon source and the second amorphous carbon composite precursor.
68. The method of claim 24, wherein the coating is by any 1 of solid phase coating, liquid phase coating, or gas phase coating.
69. The method of claim 68, wherein the solid phase coating method is: and adding the second amorphous carbon composite precursor and a carbon source into a VC mixer or a fusion machine for VC mixing or fusion.
70. The method according to claim 69, wherein in the solid phase coating method, the rotation speeds of the VC mixer and the fusing machine are independently 500r/min to 3000 r/min.
71. The method of claim 69, wherein in the solid phase coating method, the VC is mixed or fused independently for not less than 15 min.
72. The method of claim 68, wherein the liquid phase coating process is: dissolving or dispersing a carbon source in a solvent, uniformly stirring, then adding a second amorphous carbon composite precursor into the obtained mixed solution, uniformly stirring, and heating to evaporate the solvent or spray-drying to obtain a solid-phase product.
73. The method of claim 72, wherein in the liquid phase coating method, the solvent is any 1 or a combination of at least 2 of tetrahydrofuran, ethanol, isopropanol, carbon disulfide, benzene, toluene or ethyl acetate.
74. The method of claim 72, wherein the spray drying conditions in the liquid phase coating process are: the frequency of the atomizer is 60 Hz-90 Hz, the rotating speed of the atomizer is 10000 rpm-50000 rpm, the inlet temperature of spray drying is 180-450 ℃, and the outlet temperature is 80-110 ℃.
75. The method according to claim 24, wherein the temperature of the second carbonization in the step (3) is 900 to 1100 ℃.
76. The method of claim 24, wherein the second carbonization time in step (3) is 1 to 8 hours.
77. The method according to claim 76, wherein the time of the second carbonization in step (3) is 2 to 4 hours.
78. The method of claim 24, wherein step (3)' the vapor phase coating method is: and (3) placing the second amorphous carbon composite precursor in a reaction furnace, introducing protective gas, heating to 600-1200 ℃, introducing gas of an organic carbon source, reacting, and cooling.
79. The method of claim 78, wherein in the gas phase coating process of step (3)', the organic carbon source is any 1 or a combination of at least 2 of hydrocarbons, ketones, or aromatic hydrocarbon derivatives having 1 to 3 rings.
80. The method of claim 78, wherein in step (3)' the vapor phase coating process, the organic carbon source is any 1 or a combination of at least 2 of methane, ethylene, acetylene, acetone, benzene, toluene, xylene, styrene, or phenol.
81. The method according to claim 78, wherein in the gas phase coating method of step (3)', the reaction furnace is a rotary kiln, and the rotation speed of the rotary kiln is 0.1r/min to 5 r/min.
82. The method as claimed in claim 78, wherein in the gas phase coating method of step (3)', the flow rate of the organic carbon source gas is 0.1L/min to 2L/min.
83. The process of claim 78, wherein in step (3)' said vapor phase coating process, the reaction is carried out under incubation conditions for an incubation time of from 0.5h to 10 h.
84. A negative electrode material, wherein the negative electrode material is the core-shell amorphous carbon-based composite material according to any one of claims 1 to 23.
85. A lithium ion battery comprising the core-shell amorphous carbon-based composite material according to claim 84.
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