CN112885998B - Silicon composite material and preparation method thereof, negative plate and lithium ion battery - Google Patents

Silicon composite material and preparation method thereof, negative plate and lithium ion battery Download PDF

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CN112885998B
CN112885998B CN202110076173.1A CN202110076173A CN112885998B CN 112885998 B CN112885998 B CN 112885998B CN 202110076173 A CN202110076173 A CN 202110076173A CN 112885998 B CN112885998 B CN 112885998B
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silicon
hole
carbon
coating layer
composite material
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CN112885998A (en
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张敏
袁号
胡大林
廖兴群
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Huizhou Highpower Technology Co Ltd
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Huizhou Highpower Technology Co Ltd
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Priority to PCT/CN2021/103975 priority patent/WO2022156152A1/en
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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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • 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
    • H01M4/134—Electrodes based on metals, Si or alloys
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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 invention discloses a silicon composite material, a preparation method thereof, a negative plate and a lithium ion battery. The silicon composite material comprises through-hole silicon and a carbon coating layer, wherein a one-dimensional carbon material is arranged in a pore channel of the through-hole silicon. The through-hole silicon provided with the one-dimensional carbon material in the pore canal is beneficial to improving the electrical conductivity of silicon particles from the inside of a silicon material. Meanwhile, the pore channel of the through-hole silicon provides a good buffer space for the material, and the volume expansion of the material is avoided. The network structure formed by the one-dimensional carbon material in the pore channel of the through-hole silicon in a staggered manner can effectively restrict the volume expansion of the silicon material, greatly stabilize the internal structure of silicon particles, solve the problem of pulverization, effectively maintain the conductive network among the silicon particles, and effectively improve the cycle performance of the battery prepared from the material. In addition, the carbon coating layer is beneficial to reducing the contact of the silicon composite material with electrolyte in the use process, thereby reducing side reaction and further improving the electronic conductivity of the silicon composite material.

Description

Silicon composite material and preparation method thereof, negative plate and lithium ion battery
Technical Field
The application relates to the technical field of lithium ion batteries, in particular to a silicon composite material, a preparation method thereof, a negative plate and a lithium ion battery.
Background
The silicon-based material (silicon-containing oxide) is considered as an ideal negative electrode material of the next generation of high-performance lithium ion battery due to the advantages of high specific capacity, moderate working potential, rich reserve and environmental friendliness. However, the wide application of the silicon-based negative electrode is severely limited by the problems that the structure of the electrode is damaged due to huge volume expansion during the charge and discharge processes, and the capacity of the battery is rapidly reduced.
Researchers make various efforts to inhibit the expansion of the silicon material and improve the conductive network of the silicon material. Such as suppressing the expansion of the silicon negative electrode by optimizing the binder, or relieving the expansion of the silicon negative electrode by improving the silicon negative electrode material and composition. In the related technology, the porous silicon hollow sphere is taken as the core, and the volume change in the charging and discharging process can be fully relieved based on the porous channel and the hollow structure and the gap between the carbon shell layer and the core, so that the stability of the structure is kept. However, the structure only solves the space problem required by the expansion of the conductive network outside the silicon and the particles, but the stability of the conductive network inside the core particles and the stability of the hollow structure still have a big problem, and the cycle performance and the safety performance need to be improved, which is not beneficial to the industrialized popularization of the silicon material.
Disclosure of Invention
The present application is directed to solving at least one of the problems in the prior art. Therefore, the application provides a silicon composite material with good cycle performance and safety performance, a preparation method thereof, a negative plate and a lithium ion battery.
In a first aspect of the present application, a silicon composite material is provided, which includes through-hole silicon and a carbon coating layer, and a one-dimensional carbon material is provided in a pore passage of the through-hole silicon.
The through hole of the through-hole silicon refers to a hole channel with a hollow hole in the silicon material, and at least one end of the hole channel extends to the surface of the silicon material. The silicon material refers to a material having a silicon element as a main component, and specifically includes, but is not limited to, crystalline silicon (e.g., single crystal silicon, polycrystalline silicon), amorphous silicon, a silicon carbon material, a silicon oxygen material, and the like, and at least one of them is selected and used, and the silicon element as the main component refers to a material having a content of at least 50wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, 95wt%, 96 wt%, 97 wt%, 98 wt%, 99 wt%, 99.9 wt%, and 99.99 wt% of the silicon element.
The one-dimensional carbon material refers to a linear carbon material having a fiber shape or a fiber-like shape, and specifically includes, but is not limited to, carbon nanotubes (such as single-walled carbon nanotubes, multi-walled carbon nanotubes, hollow carbon nanotubes), carbon fibers, carbon nanowires, carbon nanorods, and the like, and at least one of them is selected and used.
The carbon coating layer is a coating shell formed outside a through-hole silicon as a core and having a main component of carbon element. The carbon coating layer may specifically be a coating shell formed of at least one carbon material including, but not limited to: zero-dimensional carbon black, acetylene black, ketjen black, conductive carbon black (SP), fullerene, carbon quantum dot, one-dimensional carbon nanotube, carbon fiber, carbon nanowire, carbon nanorod, two-dimensional graphene, graphite alkyne, graphite thin film, and three-dimensional graphite, carbon aerogel, graphene foam, and the like.
The silicon composite material according to the embodiment of the application has at least the following beneficial effects:
the through-hole silicon provided with the one-dimensional carbon material in the pore canal provided by the embodiment of the application has the advantages that the one-dimensional carbon material has excellent electrical conductivity, high mechanical strength, tensile strength, low density and other properties, and also has certain chemical stability and thermal conductivity, and the improvement of the electrical conductivity of silicon particles from the inside of the silicon material is facilitated. Meanwhile, a plurality of pore channels of the through-hole silicon provide good buffer space for the material, and the volume expansion of the material is avoided. In addition, the network structure formed by the one-dimensional carbon material in the pore channel of the through-hole silicon in a staggered manner can effectively restrict the volume expansion of the silicon material, greatly stabilize the internal structure of silicon particles, solve the problem of pulverization, effectively maintain the conductive network among the silicon particles, improve the ionic conductivity of the material and improve the cycle performance of a battery prepared from the material. In addition, the carbon coating layer is beneficial to reducing the contact of the silicon composite material with electrolyte in the use process, thereby reducing side reaction and further improving the electronic conductivity of the silicon composite material.
In some embodiments of the present application, there is a gap between the through-hole silicon and the carbon cladding layer. The clearance is that a certain distance exists between the inner core of the through-hole silicon and the shell of the carbon coating layer, and the clearance is not formed into a composite structure in a tightly attached mode. The gap between the inner core of the through-hole silicon and the shell of the carbon coating layer is favorable for buffering the silicon material to expand outwards, so that the structure of the composite material is stabilized, and the electrochemical performance is prevented from being influenced. On the other hand, the network structure formed by the one-dimensional carbon materials in the pore channels of the through-hole silicon in a staggered mode can play a certain role in maintaining the stability of the gap between the through-hole silicon and the carbon coating layer, and therefore the service life of the battery is effectively prolonged.
In some embodiments of the present application, the one-dimensional carbon material is grown in situ within the channels. The one-dimensional carbon material grows in situ in the silicon pore channel, so that the silicon material can exert the maximum capacity, and the problem that the capacity cannot be exerted due to poor internal conductivity of the silicon material is solved.
In some embodiments of the present application, a void is provided between an inner wall of a pore channel of the through-hole silicon and the one-dimensional carbon material disposed inside the pore channel. The voids are formed by the one-dimensional carbon material and filled in the pore channels, wherein the volume of the one-dimensional carbon material is smaller than the volume of the pore channels filled in the one-dimensional carbon material, so that the pore channels are not completely filled in the one-dimensional carbon material. The one-dimensional carbon material is positioned in the pore canal of the silicon material but not around the silicon material, and the pore canal is not completely filled with the one-dimensional carbon material, so that the filled one-dimensional carbon material can greatly increase the elastic strength of the silicon material, leave a gap for inward expansion and also contain a gap for outward expansion, further inhibit pulverization of the silicon material and improve the cycle performance.
In some embodiments of the present application, the content of the through-hole silicon is 5wt% to 95wt%, the content of the one-dimensional carbon material is 1 wt% to 50wt%, and the content of the carbon coating layer is 5wt% to 45wt%, based on the total weight of the silicon composite material.
In some embodiments of the present application, the particle size of the through-hole silicon is 10nm to 100 μm, and the pore diameter (specifically, the diameter) of the through-hole silicon pore channel is 1nm to 50 μm, wherein the pore diameter of the pore channel is adapted to the particle size of the through-hole silicon, and is obviously smaller than the particle size.
In some embodiments of the present application, the one-dimensional carbon material has a diameter of 0.5nm to 200nm and a length of 10nm to 50 μm.
In some embodiments of the present application, the carbon coating layer has a thickness of 1 to 1000 nm.
In some embodiments of the present application, the gap has a thickness of 0 to 1000 nm.
In some embodiments of the present application, the through-hole silicon has a specific surface area of 0.1 to 1000m 2 /g。
In a second aspect of the present application, there is provided a method for preparing the above silicon composite material, the method comprising the steps of:
s1: placing the silicon alloy in a first acid solution, and removing part of metal in the silicon alloy to form through-hole silicon;
s2: placing the through-hole silicon in a reactor, introducing a carbon source gas and a carrier gas, and generating a one-dimensional carbon material in a pore channel of the through-hole silicon under the reaction condition of 500-1200 ℃ to obtain an intermediate product;
s3: the intermediate product is carbon coated to form a carbon coating layer.
Here, the silicon alloy means a material containing a silicon element and a metal element. The metal element in the silicon alloy may be at least one of iron, cobalt, nickel, aluminum, magnesium, copper, manganese, vanadium, niobium, and tantalum. Partial metal refers to at least 0.1%, 0.2%, 0.5%, 0.8%, 1%, 2%, 5%, 8%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 96%, 97%, 98%, 99% of the metal element in a molar ratio, based on the total molar amount of the metal element in the silicon alloy.
The carbon source gas may be an optional gas containing carbon element, and specifically, alkanes, alkynes, olefins, benzene rings, or other carbon-containing gases; such as at least one of methane, ethane, propane, butane, ethylene, propylene, butylene, acetylene, propyne, butyne, and carbon monoxide.
The carrier gas is used to provide a protective atmosphere for the reaction system of through-hole silicon, and specifically, at least one of nitrogen, helium, neon, argon, and the like may be included.
The carbon coating method may be a method well known in the art, which is optionally capable of forming a carbon coating layer on the silicon surface of the via hole, for example, a method using liquid phase deposition or vapor phase deposition. The liquid phase deposition method is to mix the intermediate product and carbon-containing solution/dispersion liquid on the surface for carbon coating, and then form a carbon coating layer through carbonization treatment. Wherein the carbon-containing solution/dispersion can be at least one of dopamine hydrochloride-tris (hydroxymethyl) aminomethane solution, one-dimensional carbon material dispersion, two-dimensional carbon material dispersion, three-dimensional carbon material dispersion, sodium carboxymethylcellulose solution, polyvinylidene fluoride solution, polyacrylic acid solution, polyacrylonitrile solution, polyethyleneimine solution, etc. The vapor deposition method comprises introducing carbon source gas and carrier gas into a reactor containing the intermediate product, and forming a carbon coating layer on the surface under high-temperature reaction conditions, wherein the carbon source gas and carrier gas can be introduced continuously after S2, so as to prolong the reaction time. The carbon source gas in this step may be an optional gas containing carbon element, specifically, alkane, alkyne, alkene, benzene ring or other carbon-containing gas; such as at least one of methane, ethane, propane, butane, ethylene, propylene, butylene, acetylene, propyne, butyne, and carbon monoxide. The carrier gas is used to provide a protective atmosphere for the reaction system of through-hole silicon, and specifically, at least one of nitrogen, helium, neon, argon, and the like may be included.
The preparation method of the silicon composite material according to the embodiment of the application has at least the following beneficial effects:
the preparation method provided by the embodiment of the application adopts a mode that the one-dimensional carbon material grows in the silicon material, and compared with external modification, the method can form a stable through hole structure, is simple to operate, and is easy for low-cost batch production.
In some embodiments of the present application, the reaction time of S2 is 0.5 to 24 hours.
In some embodiments of the present application, the carbon source gas and the carrier gas are introduced into S2 in a flow rate of 1 to 1000 ml/min.
In some embodiments of the present application, the carbon source gas in S2 accounts for 1-80% of the total gas flow.
In some embodiments of the present application, S2 or S3 further comprises: and placing the intermediate product in a second acid solution for reaction to enlarge the pore.
The pore diameter of the pore channel is further enlarged by the second acid solution, so that the one-dimensional carbon material in the pore channel and the in-situ growth are partially filled from the original full load or nearly full load filling, and gaps are reserved between the inner wall of the pore channel of the through-hole silicon and the one-dimensional carbon material in the in-situ growth, so that the volume expansion is effectively relieved when the through-hole silicon expands inwards, the pulverization is inhibited, and the cycle performance is improved.
The first acid solution and the second acid solution are each independently selected from acid solutions capable of dissolving metal elements in the silicon alloy to form a pore structure in the silicon alloy, and specific examples thereof include acid solutions such as hydrochloric acid, sulfuric acid, and nitric acid.
In some embodiments of the present application, the silicon alloy is placed in the first acid solution for 0.5 to 10 hours, and the concentration of the first acid solution is 0.1 to 5 mol/L.
In some embodiments of the present application, the second acid solution is in excess of the residual metal elements in the through-hole silicon, and excess metal particles in the through-hole silicon are removed as much as possible by the excess acid solution, so as to further enlarge the pore diameter of the pore channel.
In some embodiments of the present application, the through-hole silicon with the one-dimensional carbon material formed in the pore channel is placed in the second acid solution for 0.5 to 24 hours, and the concentration of the first acid solution is 0.1 to 5 mol/L.
In addition, it should be noted that when the metal elements remain in the through-hole silicon, the metal elements can act as a catalyst to grow the carbon source therein as a one-dimensional carbon material, and when the content of the metal elements in the through-hole silicon is low, the carbon source (including the carbon material grown in situ inside the cell and the carbon coating layer formed by coating the outside) grows as a zero-dimensional carbon material.
In some embodiments of the present application, S3 is specifically:
placing the intermediate product in a metal salt solution, and reacting to generate through-hole silicon with a metal hydroxide coating layer;
carbon coating is carried out on the through-hole silicon with the metal hydroxide coating layer to form a carbon coating layer;
and removing the metal hydroxide coating layer to form a gap between the carbon coating layer and the through-hole silicon.
According to the method, a gap is formed between the inner core of the through-hole silicon and the outer shell of the carbon coating layer, so that the volume expansion is effectively relieved when the through-hole silicon expands outwards, the pulverization is inhibited, and the cycle performance is improved.
In some embodiments of the present application, the metal salt solution is an aluminum salt, nickel salt solution.
In some embodiments of the present application, the aluminum salt is aluminum chloride, aluminum sulfate, aluminum nitrate, or the like; the nickel salt is nickel chloride, nickel sulfate, nickel chloride, etc.
In some embodiments of the present application, the method for removing the metal hydroxide coating layer is an acid removal treatment, that is, a product containing the metal hydroxide coating layer is washed in an acid solution to dissolve the metal hydroxide coating layer therein.
In a third aspect of the present application, there is provided a negative electrode sheet comprising the silicon composite described above.
In some embodiments of the present application, the negative electrode sheet includes a current collector and an active material layer on a surface of the current collector, the active material layer including the silicon composite material described above or the silicon composite material prepared by the above-described preparation method.
In some embodiments of the present application, the active material layer further includes a binder and a conductive agent.
In some embodiments of the present application, the binder is selected from at least one of polyvinylidene fluoride (PVDF), Polytetrafluoroethylene (PTFE), Polyethyleneimine (PEI), polyaniline (PAN/PANI), polyacrylic acid (PAA), polyvinyl alcohol (PVA), Polyacrylonitrile (PAN), polyethylene oxide (PEO), sodium alginate, Styrene Butadiene Rubber (SBR), sodium carboxymethylcellulose (CMC), phenolic resin, epoxy resin, or other high molecular polymer.
In some embodiments of the present application, the conductive agent includes the above-mentioned zero-dimensional, one-dimensional, two-dimensional, and three-dimensional carbon materials, and specifically, at least one of industrially common conductive agents such as Carbon Nanotubes (CNTs), carbon fibers (VGCF), conductive graphite (KS-6, SFG-6), mesocarbon microbeads (MCMB), graphene, ketjen black, Super P, acetylene black, conductive carbon black, and hard carbon may be mentioned.
In some embodiments of the present application, the thickening agent is sodium carboxymethyl cellulose (CMC).
In a fourth aspect of the present application, a lithium ion battery is provided, which includes the above negative electrode sheet.
In some embodiments of the present application, the lithium ion battery further comprises a positive electrode sheet, an electrolyte, and a separator.
Additional aspects and advantages of the present application will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the present application.
Drawings
FIG. 1 is a schematic illustration of a silicon composite of the present application.
Fig. 2 is a schematic illustration of another silicon composite of the present application.
Fig. 3 is an electron micrograph of the silicon composite material of example 1 of the present application after 500 cycles.
Fig. 4 is an electron micrograph of the silicon composite material of example 5 of the present application after 500 cycles.
Reference numerals: the structure comprises a one-dimensional carbon material 1, a pore canal 2, through hole silicon 3, a carbon coating layer 4 and a gap 5.
Detailed Description
The conception and the resulting technical effects of the present application will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, and not all embodiments, and other embodiments obtained by those skilled in the art without inventive efforts based on the embodiments of the present application belong to the protection scope of the present application.
The following detailed description of embodiments of the present application is provided for the purpose of illustration only and is not intended to be construed as a limitation of the application.
In the description of the present application, the meaning of a plurality is one or more, the meaning of a plurality is two or more, and the above, below, exceeding, etc. are understood as excluding the present number, and the above, below, within, etc. are understood as including the present number. If the first and second are described for the purpose of distinguishing technical features, they are not to be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated or implicitly indicating the precedence of the technical features indicated.
In the description of the present application, unless otherwise expressly limited, terms such as set, mounted, connected and the like should be construed broadly, and those skilled in the art can reasonably determine the specific meaning of the terms in the present application by combining the detailed contents of the technical solutions.
In the description of the present application, reference to the description of the terms "one embodiment," "some embodiments," "an illustrative embodiment," "an example," "a specific example," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present application. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
As shown in fig. 1, a silicon composite material provided by an embodiment of the present invention is shown, and the silicon composite material includes through-hole silicon 3 and a carbon coating layer 4, where the through-hole silicon 3 has a plurality of pores 2 therein, and a one-dimensional carbon material 1 is disposed in the pores 2. The one-dimensional carbon material 1 can provide a good conductive network for the through-hole silicon 3, and meanwhile, the plurality of pore channels 2 provide a good buffer space for the through-hole silicon 3, so that disconnection of the conductive network caused by volume expansion of the through-hole silicon 3 is avoided. The silicon composite material provided by the embodiment of the invention reduces the silicon particle expansion on the premise of not inhibiting the silicon lattice expansion, effectively inhibits the pulverization of silicon materials, and can greatly improve the cycle performance.
In some embodiments, at least one end of the pore channel 2 extends to the surface of the through-hole silicon 3, and the one-dimensional carbon material 1 is criss-cross penetrated in the pore channel 2. Specifically, the pore 2 may be a closed structure at one end and is located in the through-hole silicon 3; the other end is an open structure and is positioned on the surface of the silicon material and communicated with the outside. Or the pore canal 2 penetrates through the through-hole silicon 3, and two ends of the pore canal 2 are both positioned on the surface of the silicon material and are communicated with the outside.
In some embodiments, the one-dimensional carbon material 1 is a nano material composed of a two-dimensional hexagonal lattice of carbon atoms and grown in situ in the pore channels 2, and the nano structure and the interatomic bonding strength of the one-dimensional carbon material 1 enable the nano material to have excellent electrical conductivity, high mechanical strength and tensile strength, low density and other properties, and also have certain chemical stability and excellent thermal conductivity. The silicon material can exert the maximum capacity by growing in situ in the silicon pore channel, thereby avoiding the problem that the capacity cannot be exerted due to poor internal conductivity of the silicon material.
In some embodiments of the present application, there is a gap between the inner wall of the pore channel 2 and the one-dimensional carbon material 1 disposed inside the pore channel 2, and the one-dimensional carbon material 1 does not completely fill the pore channel 2. Therefore, the elastic strength of the through-hole silicon 3 can be greatly increased by the one-dimensional carbon material 1, so that a gap is left in the through-hole silicon 3 due to internal expansion, and pulverization of the through-hole silicon 3 is inhibited.
In some embodiments of the present application, the content of the through-hole silicon 3 is 5 to 95wt%, the content of the one-dimensional carbon material 1 is 1 to 50wt%, and the content of the carbon coating layer 4 is 5 to 45wt%, based on the total weight of the silicon composite material.
In some embodiments of the present application, the through-hole silicon has a specific surface area of 0.1 to 3000m 2 (ii) in terms of/g. The larger the specific surface area, the larger the number of pores 2 in the through-hole silicon 3.
In some embodiments of the present application, the particle size of the through-hole silicon 3 is 10nm to 100 μm, the diameter of the cross section of the pore channel 2 is 1nm to 50 μm, a plurality of pore channels 2 may be connected to each other or isolated from each other, and the pore channel 2 may be disposed on the surface of the through-hole silicon 3 or extend into the through-hole silicon 3.
Referring to fig. 2, another silicon composite material provided by an embodiment of the present invention is shown, the silicon composite material including through-hole silicon 3 and a carbon cladding layer 4 with a gap 5 between the through-hole silicon 3 and the carbon cladding layer 4. The through hole silicon 3 is provided with a plurality of pore canals 2, and one-dimensional carbon materials 1 are arranged in the pore canals 2. The one-dimensional carbon material 1 can provide a good conductive network for the through-hole silicon 3, and meanwhile, the plurality of pore channels 2 provide a good buffer space for the through-hole silicon 3, so that disconnection of the conductive network caused by volume expansion of the through-hole silicon 3 is avoided. The silicon composite material provided by the embodiment of the invention reduces the silicon particle expansion on the premise of not inhibiting the silicon lattice expansion, effectively inhibits the pulverization of silicon materials, and can greatly improve the cycle performance. As can be seen, there is a certain distance between the through-hole silicon 3 and the carbon coating layer 4, rather than a close fit to form a composite structure. The gap 5 arranged between the inner core of the through hole silicon 3 and the shell of the carbon coating layer 4 is beneficial to buffering the silicon material to expand to the outside, so that the structure of the composite material is stabilized, and the electrochemical performance of the material is prevented from being influenced. The network structure formed by the one-dimensional carbon materials arranged in the through-hole silicon 3 in a staggered manner can further effectively maintain the gap structure between the carbon coating layer 4 and the through-hole silicon 3, so that the service life of the battery can be further prolonged.
The embodiment of the invention also provides a negative plate which comprises the silicon composite material or the silicon composite material prepared by the preparation method of the silicon composite material. In some embodiments, the negative electrode sheet includes a current collector and an active material layer on a surface of the current collector, and the active material layer includes the silicon composite material described above or the silicon composite material prepared by the above preparation method. In some preferred modes, the raw materials of the active material layer comprise 80-95 parts of silicon composite material, 0.5-5 parts of binder, 0.5-5 parts of dispersant, 0.5-5 parts of conductive agent, 0.2-5 parts of thickener and 100-150 parts of water.
The embodiment of the invention also provides a lithium ion battery which comprises the negative plate. In some embodiments, the lithium ion battery comprises a positive plate, a negative plate and a diaphragm, wherein the negative plate is the negative plate.
The present invention will be further described with reference to specific examples.
In the following examples:
silicon alloy is purchased from Aladdin reagent, Inc., and carbon material is purchased from Shanghai fir technology, Inc.; the used binder, dispersant, conductive agent and thickener are all purchased from Aladdin reagent company Limited;
the diaphragm is a Polyethylene (PE) porous diaphragm, is a wet diaphragm produced by Shanghai Enjie New Material science and technology Limited, and has a thickness of 12 μm;
the electrolyte is a carbonic ester solution purchased from New Zebra, and the main additives are VC and FEC;
the anode material is purchased from Xiamen tungsten industry Co Ltd, and the surface density of the anode is 23mg/cm 2 The charge-discharge voltage is 3.0-4.45V, and the charge-discharge current is 0.5C/0.5C;
the current collectors were each 6 μm copper foil.
Example 1
The embodiment provides a silicon composite material, and a preparation method thereof comprises the following steps:
s1: placing a silicon-nickel alloy (the atomic ratio of silicon to nickel is 9:1) with the total content of 10mol into 1.5L of hydrochloric acid solution with the concentration of 1mol/L, soaking for 2h, removing part of metal in the silicon-nickel alloy to form through-hole silicon with a pore passage, and simultaneously, leaving some metal in the through-hole silicon as a catalyst for growing a one-dimensional carbon material;
s2: drying the through-hole silicon, placing the through-hole silicon in a tubular furnace, introducing a mixed gas of methane and nitrogen with the gas flow of 100mL/min, wherein the methane accounts for 10% of the gas flow, the nitrogen accounts for 90% of the gas flow, and generating a one-dimensional carbon material penetrating through a pore channel of the through-hole silicon in situ to obtain an intermediate product;
s3: and placing the intermediate product in 2mg/mL dopamine hydrochloride-tris (hydroxymethyl) aminomethane solution, stirring and soaking for 24h to form a carbon coating layer, further placing in excessive 2mol/L sulfuric acid solution, removing metal particles, further enlarging pore channels, and then carbonizing for 2h at 800 ℃ to prepare the silicon composite material. The structure is shown in figure 1.
The embodiment also provides a lithium ion battery, and the preparation method of the lithium ion battery comprises the following steps:
mixing the prepared silicon composite material with a conductive agent SP, a binder PAA and a thickening agent CMC in a mass ratio of 92: 3: 3: 2, mixing, adding deionized water with the mass of 1.3 times that of the silicon composite material, and uniformly stirring to prepare the cathode slurry.
And coating the negative electrode slurry on a current collector, drying and rolling to obtain the negative electrode sheet.
The negative plate is matched with a lithium cobaltate positive plate, a diaphragm, electrolyte and an aluminum plastic film, and the battery is prepared by adopting a winding process.
Example 2
The embodiment provides a silicon composite material, and the preparation method comprises the following steps:
s1: placing a silicon-aluminum-iron alloy (the atomic ratio of silicon to aluminum to iron is 6: 2: 2) with the total content of 10mol into 3L of hydrochloric acid solution with the concentration of 2mol/L, soaking for 2h, removing part of metal in the silicon-aluminum-iron alloy to form through-hole silicon with a pore channel, and simultaneously, leaving some metal in the through-hole silicon as a catalyst for growing a one-dimensional carbon material;
s2: drying the through-hole silicon, placing the through-hole silicon in a tubular furnace, introducing a mixed gas of ethylene and argon with the gas flow of 200mL/min, wherein the ethylene accounts for 10% of the gas flow, the argon accounts for 90% of the gas flow, and generating a one-dimensional carbon material penetrating through a pore channel of the through-hole silicon in situ to obtain an intermediate product;
s3: and placing the intermediate product in 2mg/mL graphene oxide dispersion liquid, stirring and dipping for 12h to form a carbon coating layer consisting of graphene oxide, further placing the carbon coating layer in an excessive 2mol/L sulfuric acid solution, removing metal particles, further enlarging pore channels, and then carrying out thermal reduction for 2h at 600 ℃ to prepare the silicon composite material. The structure is shown in figure 1.
The embodiment also provides a lithium ion battery, and the preparation method of the lithium ion battery comprises the following steps:
mixing the prepared silicon composite material with a conductive agent SP, a binder PAA and a thickening agent CMC in a mass ratio of 92: 3: 3: 2, mixing, adding deionized water with the mass of 1.3 times that of the silicon composite material, and uniformly stirring to prepare the cathode slurry.
And coating the negative electrode slurry on a current collector, drying and rolling to obtain the negative electrode sheet.
The negative plate is matched with a lithium cobaltate positive plate, a diaphragm, electrolyte and an aluminum plastic film, and the battery is prepared by adopting a winding process.
Example 3
The embodiment provides a silicon composite material, and the preparation method comprises the following steps:
s1: placing a silicon-iron-copper alloy (the atomic ratio of silicon to iron to copper is 4: 4: 2) with the total content of 10mol into 4L of hydrochloric acid solution with the concentration of 2mol/L, soaking for 2h, removing part of metal in the silicon-iron-copper alloy to form through-hole silicon with a pore passage, and simultaneously, leaving some metal in the through-hole silicon as a catalyst for growing a one-dimensional carbon material;
s2: drying the through-hole silicon, placing the through-hole silicon in a tubular furnace, introducing a mixed gas of propylene and argon with the gas flow of 200mL/min, wherein the propylene accounts for 10% of the gas flow, the argon accounts for 90% of the gas flow, generating a one-dimensional carbon material penetrating through a pore channel of the through-hole silicon in situ to obtain an intermediate product, further placing the intermediate product in an excessive 2mol/L sulfuric acid solution, removing metal particles, and further expanding the pore channel;
s3: and placing the intermediate product into 1mg/mL carbon nanotube dispersion liquid, stirring and soaking for 24h to form a carbon coating layer consisting of the carbon nanotubes, and then drying at 60 ℃ to prepare the silicon composite material. The structure is shown in figure 1.
The embodiment also provides a lithium ion battery, and the preparation method of the lithium ion battery comprises the following steps:
mixing the prepared silicon composite material with a conductive agent SP, a binder PAA and a thickening agent CMC in a mass ratio of 92: 3: 3: 2, mixing, adding deionized water with the mass of 1.3 times that of the silicon composite material, and uniformly stirring to prepare the cathode slurry.
And coating the negative electrode slurry on a current collector, drying and rolling to obtain the negative electrode sheet.
The negative plate is matched with a lithium cobaltate positive plate, a diaphragm, electrolyte and an aluminum plastic film, and the battery is prepared by adopting a winding process.
Example 4
The embodiment provides a silicon composite material, and the preparation method comprises the following steps:
s1: placing a silicon-nickel alloy (the atomic ratio of silicon to nickel is 3: 7) with the total content of 10mol in 4L of sulfuric acid solution with the concentration of 2mol/L, soaking for 2h, removing part of metal in the silicon-nickel alloy to form through-hole silicon with a pore passage, and simultaneously, leaving some metal in the through-hole silicon as a catalyst for growing a one-dimensional carbon material;
s2: drying the through-hole silicon, placing the through-hole silicon in a tubular furnace, introducing a mixed gas of acetylene and argon with the gas flow rate of 500mL/min, wherein propylene accounts for 20% of the gas flow rate, argon accounts for 80% of the gas flow rate, generating a one-dimensional carbon material penetrating through a pore channel of the through-hole silicon in situ to obtain an intermediate product, further placing the intermediate product in an excessive 2mol/L sulfuric acid solution, removing metal particles, and further expanding the pore channel;
s3: and (3) placing the intermediate product into a mixed dispersion liquid of 1mg/mL carbon nano tube and graphene, stirring and soaking for 48 hours to form a carbon coating layer consisting of the carbon nano tube and the graphene, and then thermally reducing for 2 hours at 600 ℃ to prepare the silicon composite material. The structure is shown in figure 1.
The embodiment also provides a lithium ion battery, and the preparation method of the lithium ion battery comprises the following steps:
mixing the prepared silicon composite material with a conductive agent SP, a binder PAA and a thickening agent CMC in a mass ratio of 92: 3: 3: 2, mixing, adding deionized water with the mass of 1.3 times that of the silicon composite material, and uniformly stirring to prepare the cathode slurry.
And coating the negative electrode slurry on a current collector, drying and rolling to obtain the negative electrode sheet.
The negative plate is matched with a lithium cobaltate positive plate, a diaphragm, electrolyte and an aluminum plastic film, and the battery is prepared by adopting a winding process.
Example 5
The embodiment provides a silicon composite material, and the preparation method comprises the following steps:
s1: putting a silicon-iron-nickel alloy (the atomic ratio of silicon to iron to nickel is 8: 1: 1) with the total content of 10mol into 1.5L of hydrochloric acid solution with the concentration of 1mol/L, soaking for 2h, removing part of metal in the silicon-iron-nickel alloy to form through-hole silicon with a pore passage, and simultaneously, leaving some metal in the through-hole silicon as a catalyst for growing a one-dimensional carbon material;
s2: drying the through-hole silicon, placing the through-hole silicon in a tubular furnace, introducing a mixed gas of methane and argon with the gas flow of 100mL/min, wherein the methane accounts for 10% of the gas flow, the argon accounts for 90% of the gas flow, and generating a one-dimensional carbon material penetrating through a pore channel of the through-hole silicon in situ to obtain an intermediate product;
s3: placing the intermediate product in a solution of nickel chloride of 0.1mol/L and hexamethylenetetramine of 0.2mol/L with the volume of 1L, carrying out hydrothermal reaction for 10h at 100 ℃ to form a mixed coating layer of nickel hydroxide and a carbon source, washing, placing the obtained product in a solution of dopamine hydrochloride and trimethylolaminomethane of 10mg/mL, stirring and soaking the obtained product for 24h to form a coating layer of the carbon source, and further carbonizing the obtained product for 2h at 800 ℃ to obtain a silicon composite material with a carbon coating layer; and then placing the carbon coating layer in an excessive 2mol/L sulfuric acid solution, removing metal elements in the nickel hydroxide coating layer and the through-hole silicon, forming a gap between the carbon coating layer and the through-hole silicon, and further expanding the pore channel of the through-hole silicon to obtain the silicon composite material. The structure is shown in fig. 2.
The embodiment also provides a lithium ion battery, and the preparation method of the lithium ion battery comprises the following steps:
mixing the prepared silicon composite material with a conductive agent SP, a binder PAA and a thickening agent CMC in a mass ratio of 92: 3: 3: 2, mixing, adding deionized water with the mass of 1.3 times that of the silicon composite material, and uniformly stirring to prepare the cathode slurry.
And coating the negative electrode slurry on a current collector, drying and rolling to obtain the negative electrode sheet.
The negative plate is matched with a lithium cobaltate positive plate, a diaphragm, electrolyte and an aluminum plastic film, and the battery is prepared by adopting a winding process.
Comparative examples 1 to 5
The results were obtained in accordance with examples 1 to 5, respectively, except that no carbon coating was performed.
Comparative examples 6 to 10
The method corresponds to the embodiments 1-5 respectively, and only differs in that the one-dimensional carbon material is not grown in situ in the porous silicon.
Comparative example 11
Only difference from example 1 is that the negative active material of the battery employs single crystal silicon.
Comparative example 12
The difference from example 1 is only that the negative active material of the battery uses graphite, the gram capacity of the graphite is 365mAh/g, and the compaction density is 1.72g/cm 3 。
The negative electrode materials prepared in examples 1 to 5 and comparative examples 1 to 12 were prepared into lithium ion batteries, 5 cells were tested in each group, the energy density of the lithium ion battery at 25 ℃ and 0.5C/0.5C, the expansion rate of the negative electrode sheet after 300 cycles, the resistivity of the sheet, and the cycle number when the capacity decayed to 80% were measured by taking the average, and the test results are shown in table 1.
TABLE 1 test Performance of lithium ion batteries prepared in examples 1 to 5 and comparative examples 1 to 12
Figure BDA0002907563320000111
Figure BDA0002907563320000121
As can be seen from table 1, the silicon composite material prepared in the examples of the present application has good energy density, low expansion rate and resistivity of the pole piece, and excellent cycle life. The carbon coating layer reduces the contact between the porous silicon and the electrolyte, so that the interface side reaction is reduced, the one-dimensional carbon material is favorable for improving the electronic conductivity of the porous silicon in the porous silicon, and simultaneously inhibits the pulverization of silicon material particles, so that a skeleton effect is provided for the silicon material, and the active material is prevented from being separated from a current collector due to the pulverization. In addition, the carbon coating material and the one-dimensional carbon material have synergistic effect to further improve the conductivity of the silicon material, the carbon coating reduces the contact between the active material and the electrolyte, the cycle performance is improved, and the expansion of the silicon material is buffered by the introduction of the porous structure, so that the silicon material prepared by the method has good application prospect. In addition, compared with examples 1-4 and example 5, the product obtained after the gap is formed between the carbon coating layer and the porous silicon has good energy density, lower expansion rate and resistivity of the pole piece and excellent cycle life. Further combining the data of examples 1-5 and comparative examples 6-10, it can be seen that compared to comparative example 10 in which the one-dimensional carbon material is not grown in situ, the cycle number is increased by the in-situ growth of example 5 much more than that of other examples in which the one-dimensional carbon material is grown in situ. The result shows that the network structure formed by the staggered one-dimensional carbon materials arranged in the porous silicon can further effectively maintain the gap structure between the carbon coating layer and the porous silicon, so that the service life of the battery can be further prolonged.
Fig. 3 and 4 are electron micrographs of the silicon composite material on the surface after 500 cycles of the batteries of example 1 and example 5, respectively. As can be seen from the figure, the carbon coating of the silicon composite material in example 1 effectively avoids particle pulverization, but the particle surface has microcracks, and the surface has a thicker SEI layer, compared with the silicon composite material in example 5, the morphology of the silicon composite material is kept good, and no obvious pulverization phenomenon occurs, and the SEI film is thinner, which is attributed to the carbon coating and the reservation of hollow voids, the carbon coating reduces the contact of the silicon material and the electrolyte, and the hollow voids buffer the volume expansion of the silicon material, and avoid particle breakage.
The present application has been described in detail with reference to the embodiments, but the present application is not limited to the embodiments described above, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present application. Furthermore, the embodiments and features of the embodiments of the present application may be combined with each other without conflict.

Claims (6)

1. The silicon composite material is characterized by comprising through-hole silicon and a carbon coating layer, wherein a one-dimensional carbon material is arranged in a pore channel of the through-hole silicon, a gap is formed between the through-hole silicon and the carbon coating layer, and a gap is formed between the inner wall of the pore channel of the through-hole silicon and the one-dimensional carbon material; the preparation method of the silicon composite material comprises the following steps:
s1: placing the silicon alloy in a first acid solution, and removing part of metal in the silicon alloy to form through-hole silicon;
s2: placing the through-hole silicon in a reactor, introducing a carbon source gas and a carrier gas, and generating a one-dimensional carbon material in a pore channel of the through-hole silicon under the reaction condition of 500-1200 ℃ to obtain an intermediate product;
s3: putting the intermediate product into a metal salt solution, and reacting to generate through-hole silicon with a metal hydroxide coating layer; carbon coating the through-hole silicon with the metal hydroxide coating layer to form a carbon coating layer; removing the metal hydroxide coating layer to form a gap between the carbon coating layer and the through-hole silicon;
wherein, the S2 or S3 further comprises the step of placing the intermediate product in a second acid solution for reaction to enlarge the pore channel.
2. The silicon composite material according to claim 1, wherein the through-hole silicon is contained in an amount of 5wt% to 95wt%, the one-dimensional carbon material is contained in an amount of 1 wt% to 50wt%, and the carbon coating layer is contained in an amount of 5wt% to 45wt%, based on the total weight of the silicon composite material.
3. The silicon composite material as claimed in claim 1, wherein the through-hole silicon has a specific surface area of 0.1 to 1000m 2 /g。
4. A method for preparing a silicon composite material according to any one of claims 1 to 3, characterized by comprising the steps of:
s1: placing the silicon alloy in a first acid solution, and removing part of metal in the silicon alloy to form through-hole silicon;
s2: placing the through-hole silicon in a reactor, introducing a carbon source gas and a carrier gas, and generating a one-dimensional carbon material in a pore channel of the through-hole silicon under the reaction condition of 500-1200 ℃ to obtain an intermediate product;
s3: placing the intermediate product in a metal salt solution, and reacting to generate through-hole silicon with a metal hydroxide coating layer; carbon coating the through-hole silicon with the metal hydroxide coating layer to form a carbon coating layer; removing the metal hydroxide coating layer to form a gap between the carbon coating layer and the through-hole silicon;
wherein, the S2 or S3 further comprises the step of placing the intermediate product in a second acid solution for reaction to enlarge the pore channel.
5. Negative electrode sheet, characterized by comprising the silicon composite material according to any one of claims 1 to 3.
6. A lithium ion battery comprising the negative electrode sheet according to claim 5.
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