CN107507972B - Preparation method of silicon-carbon negative electrode material, silicon-carbon negative electrode material and lithium ion battery - Google Patents

Preparation method of silicon-carbon negative electrode material, silicon-carbon negative electrode material and lithium ion battery Download PDF

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CN107507972B
CN107507972B CN201710759298.8A CN201710759298A CN107507972B CN 107507972 B CN107507972 B CN 107507972B CN 201710759298 A CN201710759298 A CN 201710759298A CN 107507972 B CN107507972 B CN 107507972B
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silicon
carbon
negative electrode
electrode material
carbon negative
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CN107507972A (en
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白岩
马书良
成信刚
董阳阳
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Yinlong New Energy Co Ltd
Northern Altair Nanotechnologies Co Ltd
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Yinlong New Energy Co Ltd
Northern Altair Nanotechnologies Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • 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 belongs to the technical field of lithium ion batteries, and relates to a preparation method of a silicon-carbon negative electrode material, the silicon-carbon negative electrode material and a lithium ion battery. The preparation method of the silicon-carbon negative electrode material provided by the invention comprises the following steps: taking silicon alloy powder as a raw material, and removing other metals except silicon in the silicon alloy powder by acid washing treatment to obtain porous silicon; putting porous silicon into a carbon precursor, and carrying out carbon coating treatment to form a silicon-carbon composite material with a carbon coating layer; and carbonizing the silicon-carbon composite material to obtain the silicon-carbon negative electrode material. The invention has simple process and easy operation, and the prepared silicon-carbon cathode material has the high lithium storage property of silicon materials and the high cycle stability of carbon materials, and has high specific capacity, good conductivity and good cycle performance.

Description

Preparation method of silicon-carbon negative electrode material, silicon-carbon negative electrode material and lithium ion battery
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a preparation method of a silicon-carbon negative electrode material, the silicon-carbon negative electrode material and a lithium ion battery.
Background
In the existing secondary battery system, the lithium ion battery is the most competitive secondary battery at present, both from the viewpoint of development space and from the viewpoint of technical indexes such as service life, specific energy, operating voltage and self-discharge rate. With the continuous development of electronic technology, higher requirements are also put forward on lithium ion batteries, and higher energy density, better cycle life, better high and low temperature charge and discharge performance, better safety performance and the like are required, so that the positive electrode and negative electrode materials for the lithium ion batteries are required to be further developed and perfected.
At present, most of lithium ion battery negative electrode materials in practical application are carbon materials, such as natural graphite, graphitized mesocarbon microbeads and the like. In the non-carbon negative electrode material, silicon has extremely high theoretical specific capacity and a lower lithium storage reaction voltage platform, and the silicon is widely distributed in nature, and the content of the silicon in the crust is second to that of oxygen, so the silicon-based negative electrode material is a novel high-energy material with great development prospect. However, the electronic conductivity and ionic conductivity of silicon are low, resulting in poor kinetics of electrochemical reactions; the cycle stability of ordinary pure silicon is poor. And the phase change and volume expansion of silicon in the lithiation process can generate larger stress, so that the electrode is broken and pulverized, the resistance is increased, and the cycle performance is suddenly reduced.
At present, silicon powder and a carbon source material are subjected to ball milling and mixing and then pyrolyzed to prepare a silicon-carbon composite material, so that the volume expansion phenomenon in the charging and discharging processes of a battery is relieved, and the cycle performance of the silicon-based material is improved. In the existing preparation process of silicon-carbon cathode materials, two methods are commonly used: firstly, preparing a three-dimensional porous silicon material by adopting a method of inducing chemical corrosion by adopting metal silver as a catalyst, then mixing the three-dimensional porous silicon material with a carbon source by a ball milling method, and sintering to obtain a carbon-coated silicon-carbon material; and secondly, sintering the silicon monoxide under the argon condition, generating silicon and silicon dioxide by utilizing the disproportionation reaction of the silicon monoxide, preparing porous silicon by an etching method, and finally, uniformly mixing the obtained mixture and a carbon source according to a certain mass ratio and then roasting. However, the existing preparation method of silicon-carbon cathode material has certain disadvantages, such as high cost of using noble metal as catalyst, high cost of silicon monoxide, etc.; in addition, the method has complex operation steps, difficult control of the reaction process and poor stability, and is not obvious for improving the volume expansion phenomenon of silicon during charging and discharging.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a preparation method of a silicon-carbon negative electrode material, which has simple process and easy operation, and the prepared silicon-carbon negative electrode material has the high lithium storage characteristics of silicon materials and the high cycle stability of carbon materials, effectively inhibits the volume expansion of a silicon negative electrode, and has high specific capacity and long cycle life.
The second purpose of the invention is to provide a silicon-carbon negative electrode material, which can effectively inhibit the volume expansion of a silicon negative electrode, has excellent conductivity, high specific capacity and good cycle performance.
A third object of the present invention is to provide a lithium ion battery having a high specific capacity, a good cycle performance, and an excellent electrochemical performance.
In order to achieve the purpose, the invention adopts the technical scheme that:
according to one aspect of the present invention, the present invention provides a method for preparing a silicon-carbon anode material, comprising the steps of:
taking silicon alloy powder as a raw material, and removing other metals except silicon in the silicon alloy powder by acid washing treatment to obtain porous silicon;
putting the porous silicon into a carbon precursor, and carrying out carbon coating treatment to form a silicon-carbon composite material with a carbon coating layer;
and carbonizing the silicon-carbon composite material to obtain the silicon-carbon negative electrode material.
As a further preferred technical solution, the silicon alloy is one or a combination of at least two of silicon-aluminum alloy, silicon-iron alloy, silicon-magnesium alloy, silicon-copper alloy, silicon-nickel alloy and silicon-manganese alloy, preferably one or a combination of at least two of silicon-aluminum alloy, silicon-iron alloy and silicon-magnesium alloy, and more preferably silicon-aluminum alloy;
preferably, the particle size range of the silicon alloy powder is 20-70 μm, preferably 30-60 μm, and more preferably 35-55 μm;
preferably, the mass fraction of silicon in the silicon alloy powder is 5% to 20%, preferably 8% to 15%, and more preferably 10% to 13%.
As a further preferable technical proposal, before the acid washing treatment, the method also comprises a step of crushing the raw materials;
preferably, the raw materials are pulverized by adopting a jet milling mode;
preferably, pre-crushing is carried out before jet crushing, and the rotation speed of the pre-crushing is 200-300 rpm;
preferably, the air inlet pressure of the jet milling is 0.4-0.6 Mpa, and the milling pressure is 0.6-0.8 Mpa;
preferably, the particle size of the powder obtained after the jet milling is 8-15 μm.
As a further preferable technical scheme, the pickling treatment comprises primary pickling, filtering and rinsing;
preferably, the acid washing treatment comprises primary acid washing, filtering, secondary acid washing and rinsing;
preferably, one or a combination of at least two of hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid and acetic acid solution with the mass concentration of 2-20% is adopted in the primary pickling, and the primary pickling time is 10-60 min;
preferably, in the filtering step, the pore size of the filtering substrate is 0.5-3 μm;
preferably, the secondary acid washing is one of a hydrofluoric acid solution with the mass concentration of 3-20%, a mixed solution of hydrofluoric acid and hydrogen peroxide or a mixed solution of hydrofluoric acid and nitric acid, and the time of the secondary acid washing is 5-30 min;
preferably, deionized water, pure water or distilled water is used for rinsing;
preferably, the rinsing step is followed by a drying step, wherein the drying temperature is preferably 80-100 ℃.
As a further preferable technical solution, the carbon precursor includes any one or a combination of at least two of polyvinyl alcohol, polyvinyl chloride, styrene-butadiene rubber latex, polymethyl methacrylate, polyacrylonitrile, phenolic resin, pitch, glucose, sucrose, cellulose, epoxy resin, and starch.
As a further preferable technical solution, the carbon coating treatment comprises the steps of:
and (3) mixing the porous silicon precursor and the carbon precursor according to the ratio of 1: 6-10, stirring for 60-90 min, performing ultrasonic dispersion for 30-60 min, and drying to obtain a silicon-carbon composite material with a carbon coating layer;
preferably, magnetic stirring is adopted for stirring, and the stirring temperature is 20-30 ℃;
preferably, the drying adopts spray drying, the pressure of the spray drying is 0.2-0.4 Mpa, the inlet temperature is 180-240 ℃, and the outlet temperature is 120-180 ℃.
As a further preferable technical solution, the carbonization treatment includes the steps of:
and (3) placing the silicon-carbon composite material in a heating device, purifying for 30-60 min under a protective atmosphere, heating to 800-1000 ℃ at a heating rate of 5-10 ℃/min, preserving heat for 1-3 h, and cooling to room temperature to obtain the silicon-carbon negative electrode material.
As a further preferable technical scheme, the heating device is one of a tube furnace, a rotary furnace, a box furnace or a roller kiln;
preferably, the protective atmosphere is one of nitrogen, helium, neon, argon, hydrogen or argon-hydrogen mixture;
preferably, the flow rate of the protective atmosphere is 40-60 mL/min.
According to another aspect of the invention, the invention also provides a silicon-carbon negative electrode material prepared by the preparation method of the silicon-carbon negative electrode material.
According to another aspect of the present invention, the present invention also provides a lithium ion battery comprising a negative electrode comprising the above silicon carbon negative electrode material.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, the porous honeycomb silicon-carbon negative electrode material is prepared by taking the silicon alloy as a raw material and carrying out acid pickling treatment, carbon coating treatment and carbonization treatment, so that the volume effect in the charging and discharging process is relieved, and the phenomenon of pulverization and falling off of electroactive substances is reduced, thereby effectively improving the cycle stability of the lithium ion battery and prolonging the service life; meanwhile, the conductivity of the silicon-based material is improved, and the reversible specific capacity of the material is improved.
2. The method has the advantages of low cost of raw materials, environmental friendliness, easy operation and control of the preparation process, simple and feasible process conditions and low energy consumption, and the prepared silicon-carbon negative electrode material has the high lithium storage property of silicon materials and the high cycle stability of carbon materials, has good conductivity, high specific capacity and good reaction kinetics performance, is easy to realize industrialization, and has good application prospect in lithium ion batteries.
3. The lithium ion battery and the silicon-carbon cathode material provided by the invention have the advantages of low cost, stable performance, high specific capacity, good conductivity, long cycle life and excellent electrochemical performance.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is an SEM (Scanning Electron Microscope) image of the silicon-carbon negative electrode material provided in embodiment 3 of the present invention; FIGS. 1(a) and 1(b) are SEM images of porous silicon obtained by acid washing and silicon carbon negative electrode material obtained by carbonization, respectively;
FIG. 2 is a graph of cycle number-specific discharge capacity of a lithium ion battery made of the silicon-carbon negative electrode material prepared in example 3 of the present invention, wherein the abscissa represents the cycle number and the ordinate represents the specific discharge capacity (mAh. g)－1)。
Detailed Description
Embodiments of the present invention will be described in detail below with reference to embodiments and examples, but those skilled in the art will understand that the following embodiments and examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The specification of the conditions is carried out according to the conventional conditions or the conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
In a first aspect, the present embodiment provides a method for preparing a silicon-carbon anode material, including the following steps:
taking silicon alloy powder as a raw material, and removing other metals except silicon in the silicon alloy powder by acid washing treatment to obtain porous silicon;
putting the porous silicon into a carbon precursor, and carrying out carbon coating treatment to form a silicon-carbon composite material with a carbon coating layer;
and carbonizing the silicon-carbon composite material to obtain the silicon-carbon negative electrode material.
The silicon-carbon cathode material prepared by the preparation method of the silicon-carbon cathode material provided by the invention can overcome the defect that the silicon material and the carbon material which are independently used as the cathode material of the lithium ion battery in the prior art can not meet the requirement, can fully exert the functions of silicon and carbon, and has better structural stability. On one hand, the excellent conductivity of the carbon layer is utilized, the problem of poor conductivity of silicon particles is solved, and the conductivity of the material is improved; on the other hand, an electrochemical reaction interface is increased through the silicon matrix material, the electrochemical reaction dynamic performance of the material is improved, the cycle performance of the electrode is improved, silicon nuclei can be prevented from being broken and scattered, the composite material is effectively prevented from being broken and smashed due to volume change in the charging and discharging processes, the silicon volume effect is improved, and the structural stability of the material is ensured. In addition, the surface of the silicon substrate material is uniformly loaded with the carbon layer, so that the surface structure of silicon can be improved, the direct contact between the silicon and electrolyte is reduced, a stable, thin and compact solid electrolyte membrane is promoted to be formed on the surface of the electrode, the interface compatibility of the electrode/electrolyte is improved, and the cycle performance of the electrode is further improved.
The invention takes silicon alloy powder as raw material, and the silicon alloy powder is preferably silicon alloy powder which is widely applied in the market and mature in preparation process. Compared with the mode of taking noble metal as a catalyst and the like in the prior art, the method has the advantages of low raw material cost, easier control of the operation process, simplicity, practicability, environmental friendliness and low energy consumption.
The invention carries out acid cleaning treatment on the silicon alloy powder, on one hand, other metals except silicon in the silicon alloy are dissolved in acid, but the silicon is not dissolved in the acid, and then other metals except the silicon in the silicon alloy are removed, on the other hand, the porous silicon powder is prepared by the way of corroding the silicon by the acid. And then carrying out carbon coating on the obtained porous silicon to form a silicon-carbon composite material with a carbon coating layer, and then carrying out high-temperature carbonization treatment to obtain the carbon-silicon negative electrode material. Thereby solving the problems of complex preparation process, high cost, undesirable effect and the like of the existing silicon-carbon composite material.
In an alternative embodiment, the silicon alloy is one or a combination of at least two of silicon-aluminum alloy, silicon-iron alloy, silicon-magnesium alloy, silicon-copper alloy, silicon-nickel alloy and silicon-manganese alloy, preferably one or a combination of at least two of silicon-aluminum alloy, silicon-iron alloy and silicon-magnesium alloy, and further preferably silicon-aluminum alloy;
preferably, the particle size range of the silicon alloy powder is 20-70 μm, preferably 30-60 μm, and more preferably 35-55 μm;
preferably, the mass fraction of silicon in the silicon alloy powder is 5% to 20%, preferably 8% to 15%, and more preferably 10% to 13%.
The silicon alloy in the invention is a commercially available silicon alloy, preferably a eutectic silicon-aluminum alloy which is widely applied and mature in preparation process on the market, and has the characteristics of wide and easily available raw material source, low cost and easiness in subsequent operation.
In one embodiment, the silicon alloy powder optionally has a particle size of 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, or 70 μm.
In a specific embodiment, optionally, the mass fraction of silicon in the silicon alloy powder is 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, or 20%.
In an alternative embodiment, before the acid washing treatment, the method further comprises a step of crushing the raw material;
preferably, the raw materials are pulverized by adopting a jet milling mode;
preferably, the jet milling is carried out before the jet milling, the rotating speed of the pre-milling is 200-300 rpm, the air inlet pressure of the jet milling is 0.4-0.6 MPa, and the pressure of the jet milling is 0.6-0.8 MPa;
preferably, the particle size of the powder obtained after the jet milling is 8-15 μm.
In view of the large difference in the particle size range of the commercially available silicon alloy powder, in order to further improve the effect of the subsequent treatment, the raw material needs to be further pulverized by a pulverization method to obtain the desired particle size range. The preferred mode of its crushing is jet milling, convenient operation, crushing effectual.
In one embodiment, the jet milling operation is, optionally: (1) putting raw materials into a hopper; (2) turning on a feeding motor, and adjusting the rotating speed of the double screws to be 200rpm, 250rpm or 300 rpm; (3) feeding the pre-pulverized powder into a jet milling chamber, and controlling the air inlet pressure to be 0.4Mpa, 0.5Mpa or 0.6Mpa and the pulverizing pressure to be 0.6Mpa, 0.7Mpa or 0.8 Mpa; (4) the pulverized powder was collected by a cyclone and a trap system.
In one embodiment, the particle size of the powder obtained after jet milling is optionally 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm or 15 μm. The desired particle size range of the powder can be obtained by adjusting the pressure of the jet milling.
In an alternative embodiment, the pickling treatment comprises a single pickling, filtration and rinsing;
preferably, the acid washing treatment comprises primary acid washing, filtering, secondary acid washing and rinsing;
preferably, one or a combination of at least two of hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid and acetic acid solution with the mass concentration of 2-20% is adopted for primary pickling, the time for primary pickling is 10-60 min, hydrochloric acid or sulfuric acid with the mass concentration of 8-15% is preferably adopted, and the time for primary pickling is preferably 15-30 min;
preferably, in the filtering step, the pore size of the filtering substrate ranges from 0.5 to 3 μm, and preferably ranges from 1 to 2 μm;
preferably, the secondary acid washing is one of a hydrofluoric acid solution with the mass concentration of 3-20%, a mixed solution of hydrofluoric acid and hydrogen peroxide or a mixed solution of hydrofluoric acid and nitric acid, and the time of the secondary acid washing is 5-30 min;
preferably, deionized water, pure water or distilled water is used for rinsing;
preferably, the rinsing step is followed by a drying step, wherein the drying temperature is preferably 80-100 ℃.
The acid washing treatment of the present invention may include the steps of primary acid washing, filtering and rinsing, and may further include secondary acid washing in order to further improve the purity of the porous silicon produced, and the secondary acid washing is performed before the rinsing, i.e., the acid washing treatment includes the steps of primary acid washing, filtering, secondary acid washing and rinsing. Wherein, the types of the acid used for the primary acid washing and the secondary acid washing are different, so that the rest metal elements in the silicon alloy can be more effectively removed, and the purity of the porous silicon can be improved.
In one embodiment, optionally, the acid washing treatment step specifically comprises: (1) placing the powder obtained by airflow pulverization into 2%, 5%, 8%, 10%, 15% or 20% hydrochloric acid, sulfuric acid or phosphoric acid solution, and performing acid washing for 10min, 15min, 20min, 25min, 30min, 40min, 50min or 60 min; (2) filtering with filter matrix (such as filter paper) with pore diameter of 0.5 μm, 1 μm, 1.5 μm, 2 μm or 3 μm; (3) rinsing with deionized water, pure water or distilled water; (4) drying in a vacuum drying oven at 80 deg.C, 90 deg.C or 100 deg.C.
In one embodiment, optionally, the acid washing treatment step specifically comprises: (1) placing the powder obtained by airflow pulverization into 2%, 5%, 8%, 10%, 15% or 20% hydrochloric acid, sulfuric acid or phosphoric acid solution, and performing acid washing for 10min, 15min, 20min, 25min, 30min, 40min, 50min or 60 min; (2) filtering with filter matrix (such as filter paper) with pore diameter of 0.5 μm, 1 μm, 1.5 μm, 2 μm or 3 μm; (3) performing secondary acid cleaning for 5min, 10min, 15min, 20min, 25min or 30min by adopting a hydrofluoric acid solution with the mass concentration of 3%, 5%, 10%, 15% or 20%, a mixed solution of hydrofluoric acid and hydrogen peroxide or a mixed solution of hydrofluoric acid and nitric acid; (4) rinsing with deionized water, pure water or distilled water; (5) drying in a vacuum drying oven at 80 deg.C, 90 deg.C or 100 deg.C.
In an alternative embodiment, the carbon precursor includes any one of polyvinyl alcohol, polyvinyl chloride, styrene-butadiene rubber latex, polymethyl methacrylate, polyacrylonitrile, phenol resin, pitch, glucose, sucrose, cellulose, epoxy resin, starch, or a combination of at least two thereof.
Preferably, the carbon precursor is one of pitch, glucose, sucrose, cellulose or starch.
The carbon precursor and the solvent are prepared into a carbon precursor solution, wherein the solvent can be selected according to the carbon precursor, and can be selected and prepared according to the prior art as long as the carbon precursor can be dissolved.
In an optional embodiment, the carbon coating treatment step specifically includes:
and (3) mixing the porous silicon precursor and the carbon precursor according to the ratio of 1: 6-10, stirring for 60-90 min, performing ultrasonic dispersion for 30-60 min, and drying to obtain a silicon-carbon composite material with a carbon coating layer;
preferably, magnetic stirring is adopted for stirring, and the stirring temperature is 20-30 ℃;
preferably, the drying adopts spray drying, the pressure of the spray drying is 0.2-0.4 Mpa, the inlet temperature is 180-240 ℃, and the outlet temperature is 120-180 ℃.
The purpose of the carbon coating is to form a carbon coating layer on the surface of the porous silicon, thereby forming a composite material.
In one embodiment, optionally, the carbon coating treatment step specifically includes: (1) mixing porous silicon and carbon precursors according to the ratio of 1: 6. 1: 7. 1: 8. 1: 9 or 1: 10, performing magnetic stirring for 60min, 70min, 80min or 90min at the temperature of 20-30 ℃ (room temperature), performing ultrasonic dispersion for 30min, 40min, 50min or 60min, and (2) drying by adopting a spray drying mode, wherein the spray drying pressure is 0.2Mpa, 0.3Mpa or 0.4Mpa, the inlet temperature is 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃ or 240 ℃, and the outlet temperature is 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃ or 180 ℃, so as to obtain the silicon-carbon composite material with the carbon coating layer.
In an optional embodiment, the carbonizing step specifically includes:
and (3) placing the silicon-carbon composite material in a heating device, purifying for 30-60 min under a protective atmosphere, heating to 800-1000 ℃ at a heating rate of 5-10 ℃/min, preserving heat for 1-3 h, and cooling to room temperature to obtain the silicon-carbon negative electrode material.
In an alternative embodiment, the heating device is one of a tube furnace, a rotary furnace, a box furnace or a roller kiln;
preferably, the protective atmosphere is one of nitrogen, helium, neon, argon, hydrogen or argon-hydrogen mixture;
preferably, the flow rate of the protective atmosphere is 40-60 mL/min.
The aim of carbonizing treatment is to improve the strength of the composite material and optimize the porous structure of the composite material so as to obtain a porous honeycomb silicon-carbon negative electrode material; the volume effect of the silicon-based material is effectively relieved, and the cycle performance of the material is improved; and the prepared material has good structural stability and dynamic performance.
In one embodiment, optionally, the carbonization treatment step specifically includes: (1) placing the silicon-carbon composite material in a tube furnace, a rotary furnace, a box furnace or a roller kiln, and purifying for 30min, 40min, 50min or 60min under the protective atmosphere of nitrogen, helium, neon and the like; (2) heating to 800 ℃, 900 ℃, 1000 ℃ or 1100 ℃ at the heating rate of 5 ℃/min, 6 ℃/min, 7 ℃/min, 8 ℃/min, 9 ℃/min or 10 ℃/min, preserving the heat for 1h, 2h or 3h, cooling to room temperature, and carrying out the whole process under a protective atmosphere to obtain the silicon-carbon cathode material.
The cooling to room temperature is preferably carried out by natural cooling.
In a second aspect, the present embodiment provides a silicon-carbon negative electrode material, which is prepared by the above-described preparation method of the silicon-carbon negative electrode material.
In a third aspect, the present embodiment provides a lithium ion battery, including a positive electrode, a negative electrode, a separator, and an electrolyte, where the negative electrode includes the above-described silicon carbon negative electrode material.
In the second and third aspects of the present embodiment, the lithium ion battery negative electrode material may refer to the prior art for the remaining components and structure, except for using the above silicon carbon negative electrode material as an active material; the anode, the cathode and the lithium ion battery structure and the preparation method thereof can refer to the conventional technology, and the difference from the conventional technology is only that the silicon-carbon anode material obtained by the preparation method of the silicon-carbon anode material in the first aspect is added into the lithium ion battery anode material.
The silicon-carbon cathode material prepared by the technical scheme has better electrochemical performance, is used as a cathode material of a lithium ion battery, and has the advantages of low cost, stable performance, good conductivity, high specific capacity and long cycle life.
The lithium ion battery and the silicon-carbon cathode material have the advantages of low cost, stable performance, high specific capacity, good conductivity, long cycle life and excellent electrochemical performance. By using the technical scheme, the average particle size of the prepared silicon-carbon negative electrode material is 80-150 nm, the first charge-discharge specific capacity at room temperature is about 900 mA.h/g, and the reversible specific capacity is about 720mAh/g after 20 cycles.
The present invention will be further described with reference to specific examples, comparative examples and the accompanying drawings.
Example 1
A preparation method of a silicon-carbon negative electrode material comprises the following steps:
(a) acid pickling treatment: silicon-aluminum alloy powder is used as a raw material, the particle size of the silicon-aluminum alloy powder is 55 mu m, and the mass fraction of silicon in the silicon-aluminum alloy powder is 13%; firstly, carrying out primary acid washing for 20min by adopting a hydrochloric acid solution with the mass concentration of 10%; then filtering by adopting a filtering substrate with the aperture of 1 mu m; then rinsing with deionized water; finally, drying at 100 ℃, thereby removing aluminum in the silicon-aluminum alloy powder and obtaining porous silicon;
(b) carbon coating treatment: putting the obtained porous silicon into a glucose solution with the mass concentration of 10%, wherein the mass ratio of the porous silicon to the glucose solution is 1: 8, stirring for 60min, performing ultrasonic dispersion for 30min, and drying at 180 ℃ to form the silicon-carbon composite material with the carbon coating layer;
(c) carbonizing treatment: and (3) placing the obtained silicon-carbon composite material in a tubular furnace, purifying for 30min under a nitrogen atmosphere, heating to 900 ℃ at a heating rate of 8 ℃/min, preserving heat for 2h, and cooling to room temperature to obtain the silicon-carbon negative electrode material.
Example 2
A preparation method of a silicon-carbon negative electrode material comprises the following steps:
(a) acid pickling treatment: silicon-aluminum alloy powder is used as a raw material, the particle size of the silicon-aluminum alloy powder is 35 mu m, and the mass fraction of silicon in the silicon-aluminum alloy powder is 10%; firstly, carrying out primary acid washing for 30min by adopting a hydrochloric acid solution with the mass concentration of 10%; then filtering by adopting a filtering substrate with the aperture of 2 mu m; then rinsing with deionized water; finally, drying at the temperature of 80 ℃, thereby removing aluminum in the silicon-aluminum alloy powder and obtaining porous silicon;
(b) carbon coating treatment: putting the obtained porous silicon into a glucose solution with the mass concentration of 10%, wherein the mass ratio of the porous silicon to the glucose solution is 1: stirring for 90min, performing ultrasonic dispersion for 60min, and drying at 150 ℃ to form a silicon-carbon composite material with a carbon coating layer;
(c) carbonizing treatment: and (3) placing the obtained silicon-carbon composite material in a tubular furnace, purifying for 60min under a nitrogen atmosphere, heating to 1000 ℃ at a heating rate of 10 ℃/min, preserving heat for 1h, and cooling to room temperature to obtain the silicon-carbon negative electrode material.
Example 3
A preparation method of a silicon-carbon negative electrode material comprises the following steps:
(a) pretreatment of raw materials: silicon-aluminum alloy powder is used as a raw material, the particle size of the silicon-aluminum alloy powder is 50 mu m, and the mass fraction of silicon in the silicon-aluminum alloy powder is 12%; crushing the raw materials by adopting a jet milling mode, wherein the air inlet pressure is 0.4Mpa, the crushing pressure is 0.6Mpa, and the particle size of the powder obtained after crushing is 15 mu m;
(b) acid pickling treatment: firstly, carrying out primary acid washing for 20min by adopting a hydrochloric acid solution with the mass concentration of 10%; then filtering by adopting a filtering substrate with the aperture of 1 mu m; then rinsing with deionized water; finally, vacuum drying is carried out at the temperature of 100 ℃, so that aluminum in the silicon-aluminum alloy powder is removed, and porous silicon is obtained;
(c) carbon coating treatment: putting the obtained porous silicon into a glucose solution with the mass concentration of 10%, wherein the mass ratio of the porous silicon to the glucose solution is 1: 8, magnetically stirring at room temperature for 70min, performing ultrasonic dispersion for 40min, and performing spray drying at the inlet temperature of 180 ℃ and the outlet temperature of 120 ℃ under the pressure of 0.2Mpa to form the silicon-carbon composite material with the carbon coating layer;
(d) carbonizing treatment: and (3) placing the obtained silicon-carbon composite material in a tubular furnace, purifying for 50min under a nitrogen atmosphere, heating to 950 ℃ at a heating rate of 8 ℃/min, preserving heat for 2h, cooling to room temperature, and carrying out nitrogen protection in the whole process to obtain the silicon-carbon negative electrode material.
Example 4
A preparation method of a silicon-carbon negative electrode material comprises the following steps:
(a) pretreatment of raw materials: the silicon-aluminum alloy powder is used as a raw material, the particle size of the silicon-aluminum alloy powder is 70 mu m, and the mass fraction of silicon in the silicon-aluminum alloy powder is 20%; crushing the raw materials by adopting a jet milling mode, and putting the raw materials into a hopper; then, a feeding motor is started, and the rotating speed of the double screws is adjusted to 300 rpm; feeding the powder pre-crushed by the double screws into a jet milling cavity, and controlling the air inlet pressure to be 0.6Mpa and the crushing pressure to be 0.8 Mpa; collecting the crushed powder through a cyclone separator and a trapping system; the particle size of the powder obtained after pulverization was 8 μm.
Steps (b), (c) and (d) are the same as in example 3.
Example 5
A preparation method of a silicon-carbon negative electrode material comprises the following steps:
(b) acid pickling treatment: firstly, powder obtained by jet milling is put into hydrochloric acid solution with the mass concentration of 20 percent, and primary acid washing is carried out for 10 min; then filtering by adopting a filtering substrate with the aperture of 3 mu m; then rinsing with distilled water; and finally, drying in a vacuum drying oven at the drying temperature of 90 ℃ to obtain the porous silicon.
Steps (a), (c) and (d) are the same as in example 3.
Example 6
A preparation method of a silicon-carbon negative electrode material comprises the following steps:
(b) acid pickling treatment: firstly, powder obtained by jet milling is put into a hydrochloric acid solution with the mass concentration of 5 percent, and primary acid washing is carried out for 60 min; then filtering by adopting a filtering substrate with the aperture of 0.5 mu m; carrying out secondary acid cleaning for 10min by adopting a hydrofluoric acid solution with the mass concentration of 10%; then rinsing with distilled water; and finally, drying in a vacuum drying oven at the drying temperature of 100 ℃ to obtain the porous silicon.
Steps (a), (c) and (d) are the same as in example 3.
Example 7
The preparation method of the silicon-carbon cathode material is different from that of the embodiment 6 in that sulfuric acid is adopted for primary acid cleaning, a mixed solution of hydrofluoric acid and hydrogen peroxide is adopted for secondary acid cleaning, and the rest is the same as that of the embodiment 6.
Example 8
A preparation method of a silicon-carbon negative electrode material comprises the following steps:
(c) carbon coating treatment: putting the obtained porous silicon into a sucrose solution with the mass concentration of 8%, wherein the mass ratio of the porous silicon to the sucrose solution is 1: 10, magnetically stirring at room temperature for 60min, performing ultrasonic dispersion for 60min, and performing spray drying under the pressure of 0.2Mpa at the inlet temperature of 240 ℃ and at the outlet temperature of 180 ℃ to form a silicon-carbon composite material with a carbon coating layer;
steps (a), (b) and (d) are the same as in example 3.
Example 9
The preparation method of the silicon-carbon negative electrode material is different from that of the embodiment 8 in that starch is adopted as a carbon precursor, and the rest is the same as that of the embodiment 8.
Example 10
A preparation method of a silicon-carbon negative electrode material comprises the following steps:
(d) carbonizing treatment: and (3) placing the obtained silicon-carbon composite material in a rotary furnace, purifying for 30min under a helium atmosphere, heating to 800 ℃ at a heating rate of 5 ℃/min, preserving heat for 3h, cooling to room temperature, and carrying out helium protection in the whole process, wherein the flow of helium is 40mL/min, so as to obtain the silicon-carbon negative electrode material.
Steps (a), (b) and (c) are the same as in example 3.
Example 11
The preparation method of the silicon-carbon negative electrode material is different from that of the embodiment 3 in that silicon-aluminum alloy powder is replaced by silicon-magnesium alloy powder, and the rest is the same as that of the embodiment 3.
Example 12
The preparation method of the silicon-carbon negative electrode material is different from the embodiment 3 in that the silicon-aluminum alloy powder is replaced by the silicon-iron alloy powder, and the rest is the same as the embodiment 3.
Comparative example 1
The preparation method of the silicon-carbon anode material is different from the step (a) in the embodiment 3, and the rest steps are the same as the embodiment 3.
(a) Pretreatment of raw materials: the silicon-aluminum alloy powder raw material is pretreated by adopting a ball milling mode.
Comparative example 2
The preparation method of the silicon-carbon anode material is different from the step (b) in the embodiment 3, and the rest steps are the same as the embodiment 3.
(b) Acid pickling treatment: and (3) carrying out acid etching for 20min by adopting a hydrofluoric acid solution, then washing by using water, and drying at the temperature of 100 ℃ to obtain the porous silicon.
Comparative example 3
A method for preparing a silicon-carbon negative electrode material, which is different from the embodiment 3 in the step (c), and the rest steps are the same as the embodiment 3.
(c) Carbon coating treatment: mixing porous silicon and a 10% glucose solution in a mass ratio of 1: 5 mixing and stirring for 30min, and then drying in vacuum to form the silicon-carbon composite material with the carbon coating layer.
Comparative example 4
A method for preparing a silicon-carbon negative electrode material, which is different from the embodiment 3 in the step (d), and the rest steps are the same as the embodiment 3.
(d) Carbonizing treatment: carbonizing treatment is carried out in inert atmosphere under the conditions that the carbonizing temperature is 1050 ℃ and the carbonizing time is 0.5 h.
Comparative example 5
A preparation method of a silicon-carbon cathode material adopts a method for preparing a carbon-silicon composite material by using metallic silver as a catalyst to induce chemical corrosion in the prior art.
SEM scanning test is carried out on the silicon-carbon negative electrode materials prepared in the examples and the comparative example. The details will be described only with reference to example 3. Fig. 1(a) and (b) show SEM images of the porous silicon obtained by the acid washing treatment and the silicon carbon anode material obtained by the carbonization treatment in example 3, respectively. As can be seen from FIG. 1, porous silicon is obtained after acid washing of the silicon-aluminum alloy powder raw material, and the surface appearance of the porous silicon is good; the porous silicon is further subjected to carbon coating and carbonization treatment to obtain the silicon-carbon cathode material with a honeycomb structure, and the structure can effectively relieve volume expansion in the charging and discharging process, so that the phenomenon of pulverization and falling of electroactive substances is relieved, and the cycling stability of the material is improved.
Electrochemical performance test
The silicon-carbon anode materials prepared in examples 1 to 12 and comparative examples 1 to 5 were fabricated into half cells, and the phases thereof were testedElectrochemical properties were switched off and the test results are shown in table 1. Wherein, the preparation of the half cell: the button cell is assembled by taking an active material as a positive electrode and a lithium sheet as a negative electrode, a conductive carbon Super 'p' is adopted as a conductive agent, a diaphragm is celgard2400, and 1mol/L LiPF is adopted as an electrolyte6Conductive salt and DMC: DEC: EC (wt%) ═ 1: 1: 1. The test conditions were: the charge-discharge cut-off voltage is 0.05-2V, the first reversible specific capacity is tested under the state of 0.1C, the cycle efficiency is tested for 20 times under the state of 0.2C, and the test results are shown in Table 1.
TABLE 1 electrochemical Performance test results
Figure BDA0001392518400000191
Figure BDA0001392518400000201
As can be seen from Table 1, the silicon-carbon negative electrode material provided by the invention has the advantages of high first reversible specific capacity, long cycle life and good stability; the electrochemical performance of the silicon-carbon anode materials prepared in the examples 1-12 of the invention is obviously due to the comparative examples 1-5. Specifically, the preparation method of the silicon-carbon anode material provided by the invention is superior to the existing preparation method of the silicon-carbon anode material, and the prepared silicon-carbon anode material has more excellent electrochemical performance, higher specific capacity and better cycling stability within the operation modes of raw material pretreatment and acid pickling treatment, carbon coating treatment and carbonization treatment and the operation parameter range limited by the invention.
In addition, fig. 2 shows a cycle number-discharge specific capacity graph of the silicon carbon negative electrode material in example 3. As can be further seen from fig. 2, the electrochemical indexes such as the reversible specific capacity and the cycle efficiency of the silicon-carbon negative electrode material obtained in example 3 are all at a high level. It should be noted that cycle performance spectrograms of the silicon-carbon anode materials obtained by the preparation methods of the silicon-carbon anode materials described in the other examples are substantially similar to those of fig. 2. Therefore, the silicon-carbon negative electrode material obtained by the preparation method of the silicon-carbon negative electrode material improves the cycle performance of the lithium ion battery, and has good application prospect in the lithium ion battery.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (1)

1. The preparation method of the silicon-carbon negative electrode material is characterized by comprising the following steps of:
(a) pretreatment of raw materials: silicon-aluminum alloy powder is used as a raw material, the particle size of the silicon-aluminum alloy powder is 50 mu m, and the mass fraction of silicon in the silicon-aluminum alloy powder is 12%; crushing the raw materials by adopting a jet milling mode, wherein the air inlet pressure is 0.4Mpa, the crushing pressure is 0.6Mpa, and the particle size of the powder obtained after crushing is 15 mu m;
(b) acid pickling treatment: firstly, powder obtained by jet milling is put into a hydrochloric acid solution with the mass concentration of 5 percent, and primary acid washing is carried out for 60 min; then filtering by adopting a filtering substrate with the aperture of 0.5 mu m; carrying out secondary acid cleaning for 10min by adopting a hydrofluoric acid solution with the mass concentration of 10%; then rinsing with distilled water; finally, putting the silicon wafer into a vacuum drying oven for drying at the drying temperature of 100 ℃ to obtain porous silicon;
(c) carbon coating treatment: putting the obtained porous silicon into a glucose solution with the mass concentration of 10%, wherein the mass ratio of the porous silicon to the glucose solution is 1: 8, magnetically stirring at room temperature for 70min, performing ultrasonic dispersion for 40min, and performing spray drying at the inlet temperature of 180 ℃ and the outlet temperature of 120 ℃ under the pressure of 0.2Mpa to form the silicon-carbon composite material with the carbon coating layer;
(d) carbonizing treatment: and (3) placing the obtained silicon-carbon composite material in a tubular furnace, purifying for 50min under a nitrogen atmosphere, heating to 950 ℃ at a heating rate of 8 ℃/min, preserving heat for 2h, cooling to room temperature, and carrying out nitrogen protection in the whole process to obtain the silicon-carbon negative electrode material.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104638240A (en) * 2015-02-06 2015-05-20 湖州创亚动力电池材料有限公司 Method for preparing lithium ion battery silicon carbon composite anode material and product prepared by method
CN105226285A (en) * 2014-06-19 2016-01-06 中国科学院宁波材料技术与工程研究所 A kind of porous silicon carbon composite and preparation method thereof
CN106549149A (en) * 2016-10-28 2017-03-29 浙江天能能源科技股份有限公司 A kind of preparation method and application of Si-C composite material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105226285A (en) * 2014-06-19 2016-01-06 中国科学院宁波材料技术与工程研究所 A kind of porous silicon carbon composite and preparation method thereof
CN104638240A (en) * 2015-02-06 2015-05-20 湖州创亚动力电池材料有限公司 Method for preparing lithium ion battery silicon carbon composite anode material and product prepared by method
CN106549149A (en) * 2016-10-28 2017-03-29 浙江天能能源科技股份有限公司 A kind of preparation method and application of Si-C composite material

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