CN113044828A - Porous conductive silica material, preparation method thereof and lithium ion battery - Google Patents

Porous conductive silica material, preparation method thereof and lithium ion battery Download PDF

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CN113044828A
CN113044828A CN202110288201.6A CN202110288201A CN113044828A CN 113044828 A CN113044828 A CN 113044828A CN 202110288201 A CN202110288201 A CN 202110288201A CN 113044828 A CN113044828 A CN 113044828A
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sio
porous conductive
particles
carbon
lithium ion
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梁世硕
高一琳
李冰
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Kunshan Bao Innovative Energy Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The embodiment of the application provides a porous conductive silica material, a preparation method thereof and a lithium ion battery, and relates to the field of battery materials. SiO in porous conductive silicon-oxygen materialxThe particles are provided with mutually cross-linked and through hole channels, the hole channels extend from the inside to the surface and form a plurality of openings, and the carbon coating layer is coated on the SiOxThe surface of the particles. The preparation method mainly adopts cetyl trimethyl ammonium bromide as a pore-forming agent in SiOxMicelle formation in the system, highWarm reaction of SiOxSystem is formed into SiOxThe micelle of the particles correspondingly forms a through hole which is mutually crosslinked; in SiOxThe surface of the particle is coated with carbon to form a carbon coating layer. The porous conductive silica material can be used as a lithium ion battery cathode active material, so that the volume change in the charging and discharging processes can be effectively buffered, the rate capability of the battery is improved, and the cycle life of the battery is prolonged; the preparation method is simple, environment-friendly and suitable for large-scale production.

Description

Porous conductive silica material, preparation method thereof and lithium ion battery
Technical Field
The application relates to the field of battery materials, in particular to a porous conductive silica material, a preparation method thereof and a lithium ion battery.
Background
With the increasing market demand for high energy density lithium ion batteries, the anode and cathode materials of the batteries are required to have high specific capacity. Si-based anode material (including Si, SiO)xEtc.) has a specific mass capacity of three times or more as high as that of a graphite negative electrode, and is considered to be almost indispensable for a lithium ion battery having an energy density of 300wh/kg or more. However, the existing Si-based negative electrode material has the problems of large volume expansion and poor conductivity, and the Si-based negative electrode material as a negative electrode material of a lithium ion battery can cause the cycle life and the rate performance of the lithium ion battery to be poor.
In order to solve the above problems, research institutes have continued to find some porous Si-based negative electrode materials. For example, chinese patent CN103022446B discloses a negative electrode material for a lithium ion battery, in which an inner core is made of graphite material, an intermediate layer is made of porous silica material with a nanoporous structure, and an outermost coating layer is made of organic pyrolytic carbon, the core of the three-layer composite material is made of graphite material, which has a defect of low specific capacity, and during preparation, pore-forming needs to be soaked in an acidic solution to remove metal oxides, and an acid solution can pollute the environment. The Chinese patent CN110854377A discloses a porous silica composite material, the inner core of which is silicon, the middle layer is silica and metal silicate dispersed in the silica, and the outer layer is a carbon coating layer, the three-layer composite material is prepared by adding water-soluble salt to form pores in the secondary granulation process, but primary particles are still micron or submicron-level entities, and the particle fracture phenomenon caused by volume expansion in the lithium desorption process cannot be avoided.
Disclosure of Invention
The embodiment of the application aims to provide a porous conductive silica material, a preparation method thereof and a lithium ion battery, wherein the porous conductive silica material is used as a lithium ion battery cathode active material, so that the volume change in the charge and discharge process can be effectively buffered, and the rate capability and the cycle life of the battery are improved; the preparation method is simple, environment-friendly and suitable for large-scale production.
In a first aspect, embodiments of the present application provide a porous conductive silicon oxide material comprising SiOxParticles and a carbon coating layer of which 0<x<2，SiOxThe particles have through-linked pores formed from SiOxThe interior of the particles extending to SiOxMultiple openings are formed on the surface of the particles, and a carbon coating layer is coated on the SiOxThe surface of the particles.
In the above technical solution, on the one hand, SiOxThe porous conductive silica material is used as a negative electrode active material of a lithium ion battery, and the porous structure can buffer the volume change in the lithium ion de-intercalation process and prolong the cycle life of the battery; on the other hand, SiOxThe particle surface is coated with the carbon coating, and the conductive carbon coating improves the conductivity of the material, and further improves the multiplying power performance of the battery.
In one possible implementation, SiOxAt least part of the pore channels in the particles are provided with conductive carbon materials.
In the above technical scheme, SiOxConductive carbon materials can be remained in the pore channels in the particle preparation process, the conductivity inside the particles is improved, the rate capability of the battery is further improved, and the conductive carbon materials cannot completely block SiOxThe pore canal inside the particle ensures that the electrolyte can infiltrate SiOxInside the particle.
In one possible implementation, the particle size of the porous conductive silica material is 30nm to 20 μm;
and/or the thickness of the carbon coating layer is 1-200 nm;
and/or, SiOxThe porosity of the particles is 5-70%.
In a second aspect, an embodiment of the present application provides a method for preparing a porous conductive silicon oxygen material provided in the first aspect, which includes the following steps:
cetyl trimethyl ammonium bromide is adopted as pore-forming agent in SiOxIn the systemMicelle formation and high-temperature reaction to make SiOxSystem is formed into SiOxThe micelle of the particles correspondingly forms a through hole which is mutually crosslinked;
in SiOxThe surface of the particle is coated with carbon to form a carbon coating layer.
In the technical scheme, cetyl trimethyl ammonium bromide is adopted as a pore-forming agent in SiOxMicelle is formed in the system, pore-forming in primary particles is realized, the pore-forming mode is unique, the preparation process is simple, the operation is easy, the pollution is small, and the industrial production is easy. Also, cetyl trimethylammonium bromide is in SiOxMicelle formation in the system, SiO formed correspondinglyxThe pore channels in the particles are mutually cross-linked and communicated, which is beneficial to the formation of a conductive channel and forms a communicated conductive network in the particles; the electronic conductivity of the cathode material can be further improved by the external carbon coating layer formed by carbonization, thereby being beneficial to improving the multiplying power performance of the battery and buffering SiOxVolume change during lithium deintercalation.
In one possible implementation, it comprises the following steps:
dropping ammonium hydroxide into a first solution formed by dissolving diethoxysilane, hexadecyltrimethylammonium bromide and 1, 2-bis (silyl) ethane in a first solvent, stirring for reaction at 40-85 ℃, and performing centrifugal separation to obtain SiOxParticles;
mixing SiOxAnd mixing the particles and a second solution formed by dissolving the coating polymer in a second solvent, drying, and sintering in a protective atmosphere to obtain the porous conductive silicon-oxygen material.
In the technical scheme, diethoxysilane and 1, 2-bis (silyl) ethane react at high temperature to generate SiOxAnd particles are simultaneously prepared by taking hexadecyl trimethyl ammonium bromide as a pore forming agent, so that pores are formed in the primary particles.
In a possible implementation mode, the supernatant after centrifugal separation is mixed with a first solvent and hydrochloric acid, and the mixture reacts at 40-85 ℃ to obtain recyclable hexadecyl trimethyl ammonium bromide.
In the technical scheme, the pore-forming agent is recycled, so that the production cost is reduced.
In one possible implementation, the SiO is preparedxDuring particle generation, the volume usage ratio of the ammonium hydroxide to the first solvent is 3-5: 100, volume usage ratio of diethoxysilane to the first solvent is 0.5-0.8: the volume using ratio of the 100, 1, 2-bis (silyl) ethane to the first solvent is 1-1.5: 100, the dosage ratio of the hexadecyl trimethyl ammonium bromide to the first solvent is 0.1-1.2 g: 100 ml;
and/or washing and drying a centrifugal substance obtained by centrifugal separation to obtain SiOxAnd (3) granules.
In the technical scheme, the grain diameter, the thickness of the carbon coating layer and the porosity of the product are determined by the using amount and the using amount proportion of the raw materials, and the grain diameter, the porosity and the like of the product can be controlled by adjusting the using amount and the using amount proportion of the raw materials in the specific range according to requirements, so that the method is very worthy of popularization.
In a possible implementation manner, the sintering temperature is 500-1000 ℃, and the sintering time is 0.5-10 hours.
According to the technical scheme, the carbon coating layer can be formed after sintering at a certain sintering temperature for a certain time, raw materials remained in the carbon coating layer, particularly pore-forming agents remained in internal pore channels are carbonized to form the conductive carbon material, and the conductivity of the whole material is not influenced.
In a third aspect, the present application provides a lithium ion battery, which includes a positive electrode sheet containing a positive electrode active material, a negative electrode sheet containing the porous conductive silica material provided in the first aspect, a separation film, and an electrolyte.
In one possible implementation manner, the positive electrode active material comprises one or more positive electrode active materials capable of releasing and inserting lithium ions, a positive electrode binder and a positive electrode conductive agent, the positive electrode active material is a lithium-containing compound, the lithium-containing compound comprises at least one of a lithium transition metal composite oxide or a lithium transition metal phosphate compound, and the chemical formula of the lithium transition metal composite oxide is LixAO2The chemical formula of the lithium transition metal phosphate compound is LiyBPO4Wherein A and B each represent one or more transition metalsBelongs to elements, x is more than or equal to 0.05 and less than or equal to 1.20, and y is more than or equal to 0.05 and less than or equal to 1.10;
and/or the negative plate contains porous conductive silica material, natural graphite, artificial graphite, mesophase micro carbon spheres, hard carbon, soft carbon, Li-Sn alloy, Li-Sn-O alloy, Sn, SnO and SnO2Spinel-structured lithiated TiO2-Li4Ti5O12A mixture of at least one of Li-Al alloy;
and/or the material of the isolation film is selected from at least one of polyethylene, polypropylene, polyethylene terephthalate, polyimide and aramid fiber.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments of the present application will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and that those skilled in the art can also obtain other related drawings based on the drawings without inventive efforts.
Fig. 1 is a scanning electron microscope image of a porous conductive silicon oxygen material provided in embodiment 1 of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions of the embodiments of the present application will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The porous conductive silica material, the preparation method thereof, and the lithium ion battery according to the embodiments of the present application are specifically described below.
The embodiment of the application provides a porous conductive silicon oxygen material which comprises silicon monoxide (SiO)x，0<x<2) Particles and carbon coating, SiOxThe particles have through-linked pore channels, wherein the pore channels refer to long and narrow spaces surrounded by solid bodies, and the pore channels are formed by SiOxInternal extension of the particlesTo SiOxMultiple openings are formed on the surface of the particles, and a carbon coating layer is coated on the SiOxThe surface of the particles. Generally, the SiOx particles also have a conductive carbon material in the pores, and the conductive carbon material occupies the pore space to reduce the porosity, but does not block all the pores and affect the cross-linking between the pores.
In the embodiment of the application, the porous conductive silica material has micron-scale or nanometer-scale size, and the particle size is generally 30nm to 20 μm, such as 30nm, 100nm, 500nm, 1 μm, 5 μm, 10 μm or 20 μm; the porosity of the porous conductive silica material is 5% to 70%, for example 5%, 20%, 30%, 40%, 50%, 60% or 70%; the conductive carbon coating layer is formed on the outer surface of the nano-scale, and the thickness of the carbon coating layer is generally 1-200 nm, such as 1nm, 5nm, 10nm, 20nm, 50nm, 70nm or 100nm, or 110nm, 120nm, 140nm, 150nm, 170nm or 200 nm.
The embodiment of the application also provides a preparation method of the porous conductive silicon-oxygen material, which comprises the following steps: cetyl trimethyl ammonium bromide is adopted as pore-forming agent in SiOxMicelle is formed in the system, and SiO is reacted at high temperaturexSystem is formed into SiOxThe micelle of the particles correspondingly forms a through hole which is mutually crosslinked; in SiOxThe surface of the particle is coated with carbon to form a carbon coating layer.
As a specific implementation method, the preparation method specifically comprises the following steps:
step one, dissolving appropriate amount of diethoxysilane, hexadecyl trimethyl ammonium bromide and 1, 2-bis (silyl) ethane in a first solvent, and fully stirring to form a first solution.
The first solvent may be alcohol or other solvent capable of dissolving the above raw materials, and alcohol which is easy to clean and remove and is low in price is usually selected as the first solvent.
The volume usage ratio of the diethoxysilane to the first solvent is 0.5-0.8: 100, namely adding 0.5-0.8 ml of diethoxysilane into 100ml of alcohol; the volume usage ratio of the 1, 2-bis (silyl) ethane to the first solvent is 1-1.5: 100, namely adding 1-1.5 ml of 1, 2-bis (triethoxysilyl) ethane into 100ml of alcohol; the dosage ratio of the hexadecyl trimethyl ammonium bromide to the first solvent is 0.1-1.2 g: 100ml, which is equivalent to adding 0.1-1.2 g of hexadecyl trimethyl ammonium bromide into 100ml of alcohol.
Step two, dropping ammonium hydroxide into the first solution, wherein the volume usage ratio of the ammonium hydroxide to the first solvent is 3-5: 100, fully stirring, reacting at the high temperature of 40-85 ℃, and performing centrifugal separation;
washing the white powdery centrifugate obtained by centrifugal separation with deionized water and a first solvent, and drying in vacuum to obtain SiOxParticles;
and in addition, mixing the centrifugally separated supernatant with a first solvent and hydrochloric acid, and reacting at 40-85 ℃ to obtain recyclable hexadecyl trimethyl ammonium bromide.
Dissolving a coating polymer in a second solvent to form a second solution, wherein the coating polymer is polyvinylpyrrolidone (PVP) or other polymers with certain viscosity, such as phenolic resin, and particularly, the polyvinylpyrrolidone is used as the coating polymer, so that the pyrrole nitrogen in the PVP is beneficial to the improvement of the electronic conductivity, and the rate capability of the battery is favorably improved; the second solvent may be alcohol, or may be water or another solvent capable of dissolving the coating polymer.
Step four, SiOxAnd mixing the particles and the second solution, fully stirring, drying, and sintering in a protective atmosphere, wherein the protective atmosphere is generally gases which cannot react with a sintering object, such as argon, nitrogen and the like, the sintering temperature is generally 500-1000 ℃, and the sintering time is generally 0.5-10 hours, so that the porous conductive silica material is obtained.
In addition to the above-described production of SiO by the high temperature reaction of diethoxysilane with 1, 2-bis (silyl) ethane and ammonium hydroxidexBesides the scheme of the system, other silicon-containing small molecules can be adopted to form Si or SiOxAnd (4) preparing the system.
The embodiment of the application also provides an application of the porous conductive silicon-oxygen material, and the porous conductive silicon-oxygen material is used as a negative electrode material of a battery. Especially, when the porous conductive silica material is applied to the lithium ion battery cathode material, the charge and discharge multiplying power and the cycling stability of the battery can be obviously improved.
Specifically, the embodiment of the present application further provides a lithium ion battery, which may be a lithium primary battery, a lithium ion secondary battery, a lithium polymer secondary battery or a lithium ion polymer secondary battery, and the lithium ion battery generally includes a positive electrode sheet containing a positive electrode active material capable of intercalating and deintercalating lithium ions, a negative electrode sheet containing the above porous conductive silica material as a negative electrode active material, a separation film, and an electrolyte solution having ion conductivity.
The positive electrode active material includes one or more positive electrode active materials capable of releasing lithium ions, and may further include other materials such as a positive electrode binder and a positive electrode conductive agent as needed.
The positive electrode active material is a lithium-containing compound including at least one of a lithium transition metal composite oxide or a lithium transition metal phosphate compound, thereby obtaining a high energy density. The lithium transition metal composite oxide is an oxide containing Li and one or more transition metal elements as constituent elements, and has the chemical formula of LixAO2The lithium transition metal phosphate compound is a phosphate compound containing Li and one or more transition metal elements as constituent elements, and has the chemical formula of LiyBPO4The values of x and y vary with the charge-discharge state and are generally in the ranges of 0.05. ltoreq. x.ltoreq.1.20, 0.05. ltoreq. y.ltoreq.1.10, A and B respectively represent one or more transition metal elements, and in some embodiments, the transition metal element is one or more of Co, Ni, Mn, Fe, etc., because higher voltages are thereby obtained. As an embodiment, the lithium transition metal composite oxide specifically includes LiCoO2、LiNiO2And from the formula LiNi1-x-yMnxCoyO2A complex oxide represented by; the lithium transition metal phosphate compound specifically includes LiFePO4、LiCoPO4、LiFe1-uMnuPO4(u<1) Because thereby a high battery capacity is obtained and excellent cycle characteristics are obtained.
The positive electrode active material may have a coating layer on the surface thereof, or may be mixed with another compound having a coating layer. The coating layer may comprise at least one coating element compound selected from the group consisting of oxides, carbonate oxides or hydroxycarbonates. The coating may be amorphous or crystalline. The elements included in the clad layer may include Mg, Al, Co, K, Na, Ca, Si, Ti, V, Sn, Ge, Ga, B, As, Zr, or a mixture thereof. Using these elements in the compound, the coating layer can be produced by a method that does not adversely affect (or substantially does not adversely affect) the properties of the positive electrode active material.
The positive electrode conductive agent may be a carbon material, a metal material, a conductive polymer, etc., and any conductive material may be used as the conductive agent as long as it does not cause chemical changes in the battery. The conductive agent specifically includes carbon-based materials such as natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, carbon fibers, carbon nanotubes, and the like; a metal-based material comprising metal powder or metal fibers containing one or more of copper, nickel, aluminum, or silver; conductive polymers such as polyphenylene derivatives; or mixtures thereof.
The negative electrode sheet contains the porous conductive silica material of the embodiment of the present application as a negative electrode active material, and may also contain another material as a negative electrode active material, and the specific type is not particularly limited and may be selected according to the requirement. As an implementation mode, the negative plate contains the porous conductive silica material of the embodiment of the application, and natural graphite, artificial graphite, mesophase micro carbon spheres (MCMB), hard carbon, soft carbon, Li-Sn alloy, Li-Sn-O alloy, Sn, SnO and SnO2Spinel-structured lithiated TiO2-Li4Ti5O12A mixture of at least one of Li-Al alloy and the like.
Wherein, the isolating film is selected from at least one of polyethylene, polypropylene, polyethylene terephthalate, polyimide and aramid fiber. In particular, polyethylene and polypropylene have a good effect on preventing short circuits, and the stability of the battery can be improved by the shutdown effect. In some embodiments, the polyethylene may include at least one selected from the group consisting of high density polyethylene, low density polyethylene, and ultra high molecular weight polyethylene.
In some embodiments, a porous layer may be included, the porous layer being disposed on at least one surface of the separator. The porous layer on the surface of the isolating membrane can improve the heat resistance, the oxidation resistance and the electrolyte infiltration performance of the isolating membrane and enhance the adhesion between the isolating membrane and the pole piece. The porous layer may include inorganic particles and a binder, and the inorganic particles may be selected from alumina (Al)2O3) Silicon oxide (SiO)2) Magnesium oxide (MgO), titanium oxide (TiO)2) Hafnium oxide (HfO)2) Tin oxide (SnO)2) Cerium oxide (CeO)2) Nickel oxide (NiO), zinc oxide (ZnO), calcium oxide (CaO), zirconium oxide (ZrO)2) Yttrium oxide (Y)2O3) At least one of silicon carbide (SiC), boehmite, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, and barium sulfate. The binder is at least one selected from the group consisting of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, sodium carboxymethyl cellulose, polyvinylpyrrolidone, polyvinyl ether, polymethyl methacrylate, polytetrafluoroethylene, and polyhexafluoropropylene.
The features and properties of the present application are described in further detail below with reference to examples.
Example 1
The embodiment provides a porous conductive silicon-oxygen material which is prepared according to the following preparation method:
dissolving 1ml diethoxysilane, 0.9g hexadecyl trimethyl ammonium bromide and 2ml 1, 2-bis (silyl) ethane in 150ml alcohol, then dripping 6ml ammonium hydroxide, stirring at 60 deg.C for 20 hr, centrifugally separating the suspension after reaction, washing the centrifugate with water and alcohol, and vacuum drying at 80 deg.C to obtain SiOxParticles; the supernatant obtained by centrifugation is dissolved in alcohol and then reacts with hydrochloric acid at 60 ℃ to obtain hexadecyl trimethyl ammonium bromide for recycling.
Dissolving polyvinylpyrrolidone (PVP) in alcohol or water, and adding SiOxThe particles are dried after being stirred and sintered in a high-temperature furnace with argon atmosphere at 600 DEG CObtaining the porous conductive silicon-oxygen material.
The TEM image of the porous conductive silicon oxygen material is shown in FIG. 1, and the particle size is about 400 nm.
Example 2
The embodiment provides a porous conductive silicon-oxygen material which is prepared according to the following preparation method:
dissolving 1ml diethoxysilane, 0.9g hexadecyltrimethylammonium bromide and 2ml 1, 2-bis (silyl) ethane in 150ml of alcohol, then dripping 6ml ammonium hydroxide, stirring at 60 ℃ for 12 hours, centrifugally separating the suspension after reaction, washing the centrifugate with water and alcohol, and then drying in vacuum at 80 ℃ to obtain SiOxParticles; the supernatant obtained by centrifugation is dissolved in alcohol and then reacts with hydrochloric acid at 60 ℃ to obtain hexadecyl trimethyl ammonium bromide for recycling.
Dissolving polyvinylpyrrolidone (PVP) in alcohol or water, and adding SiOxAnd stirring the particles, drying, and sintering in a high-temperature furnace at 700 ℃ in an argon atmosphere to obtain the porous conductive silica material.
Example 3
The embodiment provides a porous conductive silicon-oxygen material which is prepared according to the following preparation method:
dissolving 1ml diethoxysilane, 0.6g hexadecyltrimethylammonium bromide and 2ml 1, 2-bis (silyl) ethane in 150ml of alcohol, then dripping 6ml ammonium hydroxide, stirring at 60 ℃ for 12 hours, centrifugally separating the suspension after reaction, washing the centrifugate with water and alcohol, and then drying in vacuum at 80 ℃ to obtain SiOxParticles; the supernatant obtained by centrifugation is dissolved in alcohol and then reacts with hydrochloric acid at 60 ℃ to obtain hexadecyl trimethyl ammonium bromide for recycling.
Dissolving polyvinylpyrrolidone (PVP) in alcohol or water, and adding SiOxAnd stirring the particles, drying, and sintering in a high-temperature furnace in a nitrogen atmosphere at 600 ℃ to obtain the porous conductive silica material.
Example 4
The embodiment provides a porous conductive silicon-oxygen material which is prepared according to the following preparation method:
dissolving 1ml diethoxysilane, 0.6g hexadecyltrimethylammonium bromide and 2ml 1, 2-bis (silyl) ethane in 150ml of alcohol, then dripping 6ml ammonium hydroxide, stirring at 50 ℃ for 24 hours, centrifugally separating the suspension after reaction, washing the centrifugate with water and alcohol, and then drying in vacuum at 80 ℃ to obtain SiOxParticles; the supernatant obtained by centrifugation is dissolved in alcohol and then reacts with hydrochloric acid at 60 ℃ to obtain hexadecyl trimethyl ammonium bromide.
Dissolving polyvinylpyrrolidone (PVP) in alcohol or water, and adding SiOxAnd stirring the particles, drying, and sintering in a high-temperature furnace in a nitrogen atmosphere at 600 ℃ to obtain the porous conductive silica material.
Example 5
The embodiment provides a porous conductive silicon-oxygen material which is prepared according to the following preparation method:
dissolving 1ml diethoxysilane, 0.9g hexadecyltrimethylammonium bromide and 2ml 1, 2-bis (silyl) ethane in 150ml of alcohol, then dripping 6ml ammonium hydroxide, stirring at 60 ℃ for 12 hours, centrifugally separating the suspension after reaction, washing the centrifugate with water and alcohol, and then drying in vacuum at 100 ℃ to obtain SiOxParticles; the supernatant obtained by centrifugation is dissolved in alcohol and then reacts with hydrochloric acid at 60 ℃ to obtain hexadecyl trimethyl ammonium bromide.
Polyethylene oxide (PEO) was dissolved in acetonitrile and SiO was addedxAnd heating and stirring the particles, drying, and sintering in a high-temperature furnace with a nitrogen atmosphere at 600 ℃ to obtain the porous conductive silica material.
Example 6
This example provides a porous conductive silicon oxygen material, which is prepared by the same method as that of example 1, except that: 1.2ml of diethoxysilane, 0.9g of cetyltrimethylammonium bromide and 2.25ml of 1, 2-bis (silyl) ethane were dissolved in 150ml of alcohol, followed by dropwise addition of 4.5ml of ammonium hydroxide.
Example 7
This example provides a porous conductive silicon oxygen material, which is prepared by the same method as that of example 1, except that: 0.75ml of diethoxysilane, 0.9g of cetyltrimethylammonium bromide and 1.5ml of 1, 2-bis (silyl) ethane were dissolved in 150ml of alcohol, followed by dropwise addition of 7.5ml of ammonium hydroxide.
Example 8
This example provides a porous conductive silicon oxygen material, which is prepared by the same method as that of example 1, except that: 0.2g of cetyltrimethylammonium bromide was used.
Example 9
This example provides a porous conductive silicon oxygen material, which is prepared by the same method as that of example 1, except that: 1.5g of cetyltrimethylammonium bromide was used.
Comparative example 1
The comparative example provides a porous silica composite material, which adopts a secondary granulation mode and comprises the following specific processes:
putting silicon particles with the silicon content of 99.5 wt% and the particle size of 25mm into a roller ball mill, wherein the filling coefficient is 25%; blowing air with the temperature of 115 ℃ and the humidity of 60%, keeping the positive pressure of the ball mill at 750Pa, and keeping the negative pressure of the collecting device at 600 Pa; performing ball milling reaction at the rotating speed of 60 r/min to generate silicon oxide-coated silicon fine particles with the particle size of 25 mu m and the oxygen content of 45 wt%; the fine particles are carried out of the roller ball mill by negative pressure airflow and enter a silicon powder collecting device; mixing and granulating the collected silicon oxide-coated silicon particles, the collected metal magnesium powder, the collected mixed salt particles (the molar ratio of lithium chloride to sodium chloride is 7: 3, and the eutectic point is 570 ℃) and the collected medium-temperature asphalt according to the ratio of 1:0.2:10:1 by adopting an extrusion granulation method to obtain a composite precursor; and (3) placing the composite precursor into a burning boat and placing the burning boat in a muffle furnace, carrying out sintering reaction under argon atmosphere, heating to 700 ℃ at the speed of 5 ℃/min, reacting for 6 hours, naturally cooling, washing with deionized water to remove water-soluble composite salt in the product, drying for 24 hours at the temperature of 105 ℃ after solid-liquid separation, and carrying out ball milling, crushing and scattering to obtain the porous silica powder material.
The lithium ion battery is prepared by adopting positive plates made of different positive active materials, negative plates made of different negative active materials, diaphragms and electrode solutions, and is prepared by the following preparation processes:
LiCoO as positive electrode active material2(LCO) or LiNi0.8Co0.15Al0.05O2(NCA), a conductive agent Super P and polyvinylidene fluoride (PVDF) in a weight ratio of 96: 2: 2, mixing, adding N-methyl pyrrolidone (NMP), and uniformly stirring under the action of a vacuum stirrer to obtain anode slurry, wherein the solid content of the anode slurry is 70 wt%; and (3) uniformly coating the positive slurry on a positive current collector aluminum foil, and drying to obtain a corresponding positive plate.
The negative electrode active material graphite was mixed with the porous conductive silica material in examples 1 to 9 and the uncoated SiO in example 1xParticle mixing or the porous silica composite material (material content 15%) of comparative example 1, conductive aid Super P, sodium carboxymethylcellulose (CMC), binder Styrene Butadiene Rubber (SBR) in a weight ratio of 95: 2: 1: 2, mixing, adding deionized water, and obtaining cathode slurry under the action of a vacuum stirrer, wherein the solid content of the cathode slurry is 50 wt%; and uniformly coating the negative electrode slurry on a copper foil of a negative current collector, and drying to obtain a corresponding negative plate.
In a dry argon atmosphere glove box, Ethylene Carbonate (EC), Propylene Carbonate (PC), Ethyl Methyl Carbonate (EMC), diethyl carbonate (DEC) were mixed in the weight ratio EC: PC: EMC: DEC 25: 10: 20: 45, followed by the addition of the additives PS (2%), hexanetricarbonitrile (HTCN 1%), FEC (8%), dissolved and thoroughly stirred followed by the addition of the lithium salt LiPF6Mixing uniformly to obtain electrolyte, wherein, LiPF6The concentration of (2) is 1.1 mol/L.
A Polyethylene (PE) film having a thickness of 15 μm was used as the separator.
And (2) stacking the different positive plates, the different isolating films and the different negative plates in sequence according to the combination mode of the table 1 to enable the isolating films to be positioned between the positive plates and the negative plates to play an isolating role, then winding and welding the tabs, then placing the tabs into an outer packaging foil aluminum plastic film, drying, injecting the prepared electrolyte, and carrying out processes of vacuum packaging, standing, formation, shaping, capacity test and the like to obtain the lithium ion batteries of the first embodiment to the tenth embodiment and the first comparative embodiment to the third comparative embodiment.
Test method
(1) Lithium ion battery cycle performance test
NCA system: and (3) placing the lithium ion battery in a constant temperature box at 25 ℃, and standing for 30 minutes to keep the temperature of the lithium ion battery constant. The lithium ion battery reaching a constant temperature was charged at a constant current of 0.5C to a voltage of 4.2V, then charged at a constant voltage of 4.2V to a current of 0.05C, and then discharged at a constant current of 0.5C to a voltage of 2.75V, which is a charge-discharge cycle. Thus, the capacity retention ratio after the battery was cycled 100 times was calculated, respectively. The lithium ion battery 25 ℃ cycle test data is shown in table 1.
LCO system: and (3) placing the lithium ion battery in a constant temperature box at 25 ℃, and standing for 30 minutes to keep the temperature of the lithium ion battery constant. The lithium ion battery reaching a constant temperature is charged with a constant current of 0.5C to a voltage of 4.4V, then charged with a constant voltage of 4.4V to a current of 0.05C, and then discharged with a constant current of 0.5C to a voltage of 3V, which is a charge-discharge cycle. Thus, the capacity retention ratio after the battery was cycled 100 times was calculated, respectively. The lithium ion battery 25 ℃ cycle test data is shown in table 1.
(2) Rate capability test for lithium ion battery
NCA system: and (3) placing the lithium ion battery in a constant temperature box at 25 ℃, and standing for 30 minutes to keep the temperature of the lithium ion battery constant. And charging the lithium ion battery reaching the constant temperature to the voltage of 4.2V at a constant current of 0.5C, then charging the lithium ion battery to the current of 0.05C at a constant voltage of 4.2V, then discharging the lithium ion battery to the voltage of 2.75V at a constant current of 3C, recording the discharge capacity of the battery, and then dividing the discharge capacity by the discharge capacity of 0.5C to obtain the capacity retention rate under the condition of 3C. The lithium ion battery 25 ℃ rate test data is shown in table 1.
LCO system: and (3) placing the lithium ion battery in a constant temperature box at 25 ℃, and standing for 30 minutes to keep the temperature of the lithium ion battery constant. The lithium ion battery reaching the constant temperature is charged to the voltage of 4.4V at the constant current of 0.5C, then charged to the current of 0.05C at the constant voltage of 4.4V, then discharged to the voltage of 3V at the constant current of 3C, the discharge capacity of the battery is recorded, and then the discharge capacity is divided by the discharge capacity of 0.5C to obtain the capacity retention rate under the condition of 3C. Specific test data are shown in table 1.
Second, test results
TABLE 1 test data
Figure BDA0002980602890000141
As can be seen from comparing the first to tenth examples with the first to third comparative examples, the rate performance and cycle performance of the lithium ion battery formed by the negative active material of the example of the present application are relatively higher.
Comparing the first and second examples with the first and second comparative examples respectively, it can be seen that: the surface carbon coating contributes to the improvement of the rate capability of the battery.
Through analysis, the primary particles of the third comparative example are micron-sized solid SiOx, the primary particles are subjected to secondary granulation and agglomeration to form the porous silicon oxide composite material, and compared with the first example and the first comparative example, the performance of the third comparative example is obviously weaker than that of the first example and the first comparative example, so that when the primary particles in the negative active material are solid SiOxIn this case, the rate capability and cycle capability are further degraded.
In summary, according to the porous conductive silica material, the preparation method thereof and the lithium ion battery provided by the embodiment of the application, the porous conductive silica material can be used as a lithium ion battery cathode active material, so that the volume change in the charge and discharge processes can be effectively buffered, and the rate performance and the cycle life of the battery can be improved; the preparation method is simple, environment-friendly and suitable for large-scale production.
The above description is only an example of the present application and is not intended to limit the scope of the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims (10)

1. A porous conductive silicon-oxygen material is characterized in that the material comprises SiOxParticles and a carbon coating layer of which 0<x<2, the SiOxThe particles have through-linked pores which are cross-linked with each otherFrom the SiOxThe interior of the particles extending to the SiOxA plurality of openings are formed on the surface of the particle, and the carbon coating layer is coated on the SiOxThe surface of the particles.
2. The porous conductive silicon oxygen material of claim 1, wherein the SiO isxAt least part of the pore channels in the particles are provided with conductive carbon materials.
3. The porous conductive silicon oxygen material of claim 1, wherein the particle size of the porous conductive silicon oxygen material is 30nm to 20 μm;
and/or the thickness of the carbon coating layer is 1-200 nm;
and/or, the SiOxThe porosity of the particles is 5-70%.
4. A process for the preparation of a porous conductive silicone material according to any one of claims 1 to 3, characterized in that it comprises the following steps:
cetyl trimethyl ammonium bromide is adopted as pore-forming agent in SiOxMicelle is formed in the system, and the SiO is reacted at high temperaturexSystem is formed into SiOxThe micelle of the particles correspondingly forms a through hole which is mutually crosslinked;
in the SiOxThe surface of the particle is coated with carbon to form a carbon coating layer.
5. The method for preparing a porous conductive silicone material according to claim 4, comprising the steps of:
dropping ammonium hydroxide into a first solution formed by dissolving diethoxysilane, hexadecyltrimethylammonium bromide and 1, 2-bis (silyl) ethane in a first solvent, stirring for reaction at 40-85 ℃, and performing centrifugal separation to obtain SiOxParticles;
subjecting the SiOxMixing the particles with a second solution prepared by dissolving the coating polymer in a second solvent, drying, and sintering in a protective atmosphere to obtain the final productA porous conductive silicon oxygen material.
6. The preparation method of the porous conductive silicone material according to claim 5, wherein the centrifugally separated supernatant is mixed with the first solvent and hydrochloric acid, and the mixture is reacted at 40-85 ℃ to obtain reusable cetyl trimethyl ammonium bromide.
7. The method for preparing a porous conductive silicon oxygen material according to claim 5, wherein the SiO is preparedxWhen in particle, the volume usage ratio of the ammonium hydroxide to the first solvent is 3-5: 100, the volume usage ratio of the diethoxysilane to the first solvent is 0.5-0.8: 100, the volume usage ratio of the 1, 2-bis (silyl) ethane to the first solvent is 1-1.5: 100, the dosage ratio of the hexadecyl trimethyl ammonium bromide to the first solvent is 0.1-1.2 g: 100 ml;
and/or washing and drying a centrifugal substance obtained by centrifugal separation to obtain the SiOxAnd (3) granules.
8. The method for preparing a porous conductive silica material according to claim 5, wherein the sintering temperature is 500 to 1000 ℃ and the sintering time is 0.5 to 10 hours.
9. A lithium ion battery comprising a positive electrode sheet containing a positive electrode active material, a negative electrode sheet containing the porous conductive silicone material according to any one of claims 1 to 3, a separator, and an electrolyte.
10. The lithium ion battery according to claim 9, wherein the positive electrode active material comprises a positive electrode active material containing one or more kinds of lithium ions capable of being deintercalated, a positive electrode binder, and a positive electrode conductive agent, the positive electrode active material is a lithium-containing compound including at least one of a lithium transition metal composite oxide or a lithium transition metal phosphate compound, and the lithium transition metal composite oxide is a mixture of a lithium transition metal and a lithium transition metal phosphate compoundHas a chemical formula of LixAO2The chemical formula of the lithium transition metal phosphate compound is LiyBPO4Wherein A and B respectively represent one or more transition metal elements, x is more than or equal to 0.05 and less than or equal to 1.20, and y is more than or equal to 0.05 and less than or equal to 1.10;
and/or the negative plate contains the porous conductive silica material, natural graphite, artificial graphite, mesophase micro carbon spheres, hard carbon, soft carbon, Li-Sn alloy, Li-Sn-O alloy, Sn, SnO and SnO2Spinel-structured lithiated TiO2-Li4Ti5O12A mixture of at least one of Li-Al alloy;
and/or the material of the isolating membrane is selected from at least one of polyethylene, polypropylene, polyethylene terephthalate, polyimide and aramid fiber.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114524471A (en) * 2022-04-22 2022-05-24 宜宾锂宝新材料有限公司 Low-residual-alkali high-nickel ternary cathode material, and preparation method and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1913200A (en) * 2006-08-22 2007-02-14 深圳市贝特瑞电子材料有限公司 Silicon carbone compound negative polar material of lithium ion battery and its preparation method
CN103280560A (en) * 2013-05-20 2013-09-04 北京科技大学 Preparation method of mesoporous SiOx/C composite negative material of lithium-ion battery
CN106848264A (en) * 2017-04-01 2017-06-13 江苏中天科技股份有限公司 A kind of porous silicon oxide lithium ion battery negative material and preparation method thereof
CN109273680A (en) * 2018-08-29 2019-01-25 四川西丹孚能源科技有限公司 A kind of porous silicon-carbon cathode material and preparation method thereof and lithium ion battery

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1913200A (en) * 2006-08-22 2007-02-14 深圳市贝特瑞电子材料有限公司 Silicon carbone compound negative polar material of lithium ion battery and its preparation method
CN103280560A (en) * 2013-05-20 2013-09-04 北京科技大学 Preparation method of mesoporous SiOx/C composite negative material of lithium-ion battery
CN106848264A (en) * 2017-04-01 2017-06-13 江苏中天科技股份有限公司 A kind of porous silicon oxide lithium ion battery negative material and preparation method thereof
CN109273680A (en) * 2018-08-29 2019-01-25 四川西丹孚能源科技有限公司 A kind of porous silicon-carbon cathode material and preparation method thereof and lithium ion battery

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114524471A (en) * 2022-04-22 2022-05-24 宜宾锂宝新材料有限公司 Low-residual-alkali high-nickel ternary cathode material, and preparation method and application thereof
CN114524471B (en) * 2022-04-22 2022-07-08 宜宾锂宝新材料有限公司 Low-residual-alkali high-nickel ternary cathode material, and preparation method and application thereof

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