CN114843479A - Silicon-tin nano material and preparation method and application thereof - Google Patents

Silicon-tin nano material and preparation method and application thereof Download PDF

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Publication number
CN114843479A
CN114843479A CN202210562953.1A CN202210562953A CN114843479A CN 114843479 A CN114843479 A CN 114843479A CN 202210562953 A CN202210562953 A CN 202210562953A CN 114843479 A CN114843479 A CN 114843479A
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silicon
tin
nano material
particles
negative electrode
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CN202210562953.1A
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Inventor
吴倩
段浩杰
朱琳
徐宏强
张羽婷
何海勇
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Ningbo Institute of Material Technology and Engineering of CAS
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Ningbo Institute of Material Technology and Engineering of CAS
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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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • 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
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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 provides a silicon-tin nano material and a preparation method and application thereof. Comprises silicon particles and stannic oxide particles loaded on the surfaces of the silicon particles; the silicon particles comprise nano-silicon and/or micro-silicon; the grain size of the silicon tin nano material is 1-2 mu m. Silicon is used as a core, tin dioxide is used as a coating layer, the tin dioxide is a good conductive material, the specific capacity of the tin dioxide per se is as high as 782mAh/g, the lithium insertion potential is low, and lithium dendrite is not easily formed when the tin dioxide participates in electrode reaction. Surface oxidation of dioxide during cycling of the batteryTin reacts with lithium in the system to become Li x Sn, and a formed lithium stannide interface can better maintain structural stability, reduce the occurrence of side reactions and reduce the thickness of an SEI film, thereby effectively improving the cycle performance of the composite material. Can realize batch production and is easy for industrialized application. Compared with pure silicon, the lithium ion battery prepared by the cathode material obtained by the method has excellent electrochemical properties such as high first efficiency, high specific capacity and good cycle performance.

Description

Silicon-tin nano material and preparation method and application thereof
Technical Field
The invention relates to the field of material science, in particular to a silicon-tin nano material and a preparation method and application thereof.
Background
The lithium ion battery has the advantages of high energy density, long cycle life, environmental friendliness and the like, and is widely applied to the fields of portable electronic equipment, electric automobiles and the like. Among many lithium ion battery components, the negative electrode material is one of the main 'fierces' to ensure further improvement of energy density and cycle stability of the lithium ion battery and to lead the battery cost. Currently, the commercial negative electrode material of the lithium ion battery is mainly a graphite material, and graphite is a cheap and stable negative electrode material of the battery and is the most widely commercialized negative electrode material at present. However, the theoretical capacity of graphite is only 372mAh g -1 In recent years, the capacity of commercial graphite has reached 355-360 mAh g -1 The battery with graphite as the cathode is difficult to meet the cruising requirement of people along with the vigorous development of electric automobiles. Therefore, silicon-based anode materials have received much attention due to their higher capacity.
In the currently developed lithium ion battery cathode materials, the silicon-based materials are favored due to the lower potential and the extremely high theoretical capacity, but the silicon-based materials undergo severe volume change (the expansion rate is as high as 300%) in the process of lithium ion desorption and intercalation, so that the material structure is damaged and mechanically pulverized, the separation between electrode materials and between the electrode materials and a current collector is caused, and further the electrical contact is lost, so that the capacity is rapidly reduced. Therefore, how to improve the cycle performance of the silicon-based anode material while obtaining high capacity is a major research point at present. In order to buffer the capacity fading caused by the huge volume change of silicon in the electrochemical process, various methods are adopted to improve the cyclicity of the silicon negative electrode material. For example, patent 202120193665.9 discloses a silicon-carbon composite negative electrode material, which includes silicon-based active particles, a conductive material and a carbon coating layer. The addition of the conductive material can enhance the conductivity of the silicon-based material, and the carbon coating layer can effectively relieve the volume expansion, so that the electrochemical performance of the silicon-based negative electrode material can be enhanced to a certain extent. However, the materials are prepared through multi-step operation, and the experimental cost is high, the process variables are multiple, the commercialization difficulty is high, and the cost is high.
Disclosure of Invention
In view of the above problems, there is a need to develop a silicon-based composite negative electrode material, which not only improves the conductivity of the material to inhibit the volume expansion of the negative electrode material, but also improves the cycling stability of the material.
In view of this, the invention aims to provide a silicon-tin composite negative electrode material, a preparation method thereof and a lithium ion battery, which can effectively inhibit the volume expansion of the negative electrode material, improve the cycle performance of the battery, and have simple preparation method and can reduce the preparation cost.
According to one aspect of the present application, there is provided a silicon tin nanomaterial comprising silicon particles and tin dioxide particles;
the tin dioxide particles are loaded on the surfaces of the silicon particles;
in the silicon tin nano material, the content ratio of silicon particles to tin dioxide is 2-3: 1.
The silicon particles comprise nano-silicon and/or micro-silicon;
the grain size of the silicon tin nano material is 1-2 mu m.
The particle size of the nano silicon is 50-100 nm;
the particle size of the micron silicon is 1-5 mu m;
the particle size of the tin dioxide particles is 1-2 nm.
According to another aspect of the application, the invention provides a preparation method of the above silicon-tin nano material, which comprises a preparation method of synthesizing a silicon-tin dioxide composite negative electrode material by a high-temperature melting method.
According to another aspect of the present application, there is provided a method for preparing the above-mentioned silicon-tin nanomaterial, comprising at least the following steps:
and mixing, melting and calcining raw materials containing silicon powder and stannous chloride to obtain the silicon-tin nano material.
The mass ratio of the silicon powder to the stannous chloride is 1-3: 1. the mass ratio of the silicon powder to the stannous chloride is selected from 1: 1. 2: 1 or 3: 1.
the stannous chloride is anhydrous stannous chloride.
The melting temperature is 280-300 ℃;
the melting time is 2-3 h.
The calcining temperature is 280-300 ℃;
the calcining time is 2-3 h.
The melting and calcining atmosphere is an inert gas atmosphere;
the inactive gas is selected from at least one of nitrogen, argon, helium or neon.
The flow rate of the inactive gas is 50-150 sccm;
in the present invention, "sccm" refers to Standard Cubic Centimeter per Minute, Standard ml/min.
Specifically, the method comprises the following steps:
(1) mixing silicon particles with different particle sizes with anhydrous stannous chloride, and grinding the silicon particles in a mortar after uniformly mixing the silicon particles with different particle sizes until no granular sensation exists;
(2) carrying out high-temperature treatment on the mixture of the silicon and the stannous chloride which are uniformly ground and mixed in a tubular furnace under inert gas to change the stannous chloride into molten state;
(3) in the air, the mixture of silicon and stannous chloride (molten state) after high-temperature treatment is put into a muffle furnace for calcination, and then the target product is obtained.
The high-temperature melting method in the step (2) uses a single-temperature-zone tube furnace;
and (4) calcining in a muffle furnace in the step (3).
According to another aspect of the present application, there is provided a negative electrode material for a lithium ion battery, including the above-mentioned silicon tin nanomaterial or the silicon tin nanomaterial prepared by the above-mentioned preparation method.
The electrode material is 100mAg -1 The capacity is maintained at 2500mAh g under the current density -1 ；
At 1000mAg -1 The capacity is maintained at 1500mAhg under the current density -1 。
Compared with the prior art, the invention has the following beneficial technical effects:
1) the preparation method provided by the invention uses high-temperature melting, is a very competitive method for preparing the electrode material, and can effectively prepare the high-performance electrode material so as to meet the increasing requirements of the lithium battery cathode material; meanwhile, the preparation method has high repeatability, can easily realize batch preparation, and is suitable for industrial production.
2) After the prepared silicon-tin composite negative electrode material is used as a negative electrode material of a lithium ion battery, compared with a pure silicon negative electrode material, the first effect is greatly improved, and the cycle stability is also improved. The tin dioxide is used for coating the nano silicon particles, so that the conductivity and the cycling stability of the material are improved, and compared with a silicon-carbon negative electrode material, the material has great advantages in specific capacity. The capacity of the lithium ion battery assembled by the electrode material is maintained at 2500mAh/g under the current density of 100mA/g, and the lithium ion battery is an ideal negative electrode material of the ion battery.
Drawings
FIG. 1 is a scanning electron microscope photograph of a silicon tin nanomaterial prepared in example 1 of the present invention;
FIG. 2 is a TEM photograph of the SiSn nanomaterial prepared in example 1 of the present invention;
FIG. 3 is an X-ray diffraction pattern of a silicon-tin nanomaterial prepared in example 1 of the present invention;
FIG. 4 is a charging and discharging curve of the Si-Sn nanomaterial prepared in example 1 of the present invention as a negative electrode of a lithium ion battery;
FIG. 5 is a cycle performance curve of the Si-Sn nanomaterial prepared in example 1 of the present invention as a negative electrode of a lithium ion battery.
Detailed Description
The present invention will be further described with reference to the following detailed description and accompanying drawings, but is not limited thereto. Meanwhile, the experimental methods described in the following examples are conventional methods well known to those skilled in the art unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1:
the embodiment provides a preparation method of a nano silicon tin dioxide composite electrode material, wherein the preparation method comprises the following specific steps:
weighing 500mg of nano silicon particles (the particle size is 50-100 nm) and 250mg of anhydrous stannous chloride, and putting the nano silicon particles and the anhydrous stannous chloride into a mixer for mixing. After being mixed evenly and completely, the mixture is put into a mortar for grinding; obtaining a mixed material;
and (3) putting the mixture into a tubular furnace for high-temperature melting under an inert atmosphere (argon gas with the flow rate of 150sccm) until no granular feeling is formed after grinding. Calcining conditions are as follows: keeping the temperature at 300 ℃ for 2 h;
and (3) putting the melted mixed material into a muffle furnace for calcining, wherein the calcining conditions are as follows: and (4) preserving the heat for 2h at the temperature of 300 ℃ to obtain a sample to be detected.
The preparation process of the electrode comprises the following steps: firstly, a sample to be detected is taken as an active substance, fully ground with a conductive agent (super-P) and a binding agent (CMC) according to the mass ratio of 8:1:1, added with a proper amount of deionized water and stirred into uniform slurry. And secondly, uniformly coating the uniformly stirred slurry on the rough surface of the copper foil by using a coating machine. And (3) putting the copper foil into a blast oven for drying at 60 ℃, and then putting the copper foil into a vacuum oven for drying at constant temperature of 80 ℃ for 12 hours. And finally cutting the fully dried copper foil into a wafer with the diameter of 12mm, weighing, and drying and storing at room temperature. The surface loading of the copper foil can be ensured to be 1.2 mg-cm through adjusting the concentration of the slurry and the height of the scraper in the whole preparation process -2 Left and right. In a glove box filled with argon (H) 2 O and O 2 All volume fractions of (A) are less than 1X 10 -7 ) In the method, a button cell is assembled by taking a metal lithium sheet as a reference electrode.
The testing process comprises the following steps: the electronic stock share of the blue electricity in Wuhan City isThe battery test system CT2001A from Limited corporation was used to perform a battery capacity test. Si @ SnO for the material obtained in example 1 2 The button cell of the cathode is subjected to constant current charge and discharge capacity test, wherein the cell is subjected to constant current discharge to 0.01v at a current density of 100mA/g, then is subjected to constant current charge to 3v at the same current density, and is circulated for 5 circles. And then circulating for 100 circles at a current density of 1000 mA/g.
FIG. 1 is a scanning electron micrograph of a silicon tin nanomaterial described in example 1 of the present invention, and it can be seen that the material has a spherical granular structure, and the diameter of the spherical granules is about 100 nm.
FIG. 2 is a TEM image of the silicon-tin nanomaterial of example 1, and it can be seen from the image that the composite material has silicon nanoparticles inside, the particle size range is 50-100 nm, and the surface-supported tin dioxide coating layer has a continuous and compact structure.
FIG. 3 is an XRD diffraction pattern of the silicon-tin nano-material of example 1, in which the diffraction peaks of silicon and tin dioxide are evident and no other impurity peaks are observed.
FIG. 4 is a charge-discharge curve of the Si-Sn nanomaterial of example 1 of the present invention as a negative electrode of a lithium ion battery. It can be seen from the figure that the charge and discharge voltage plateau is low.
FIG. 5 is a diagram of the electrochemical performance of a lithium ion battery prepared by using the cathode made of the nano-silicon-tin material in example 1 of the present invention, and it can be seen that the lithium ion battery assembled by the electrode material has a current of 100mA g -1 The capacity is maintained at 2500mAh g under the current density -1 At 1000mA · g -1 The capacity is maintained at 1500mAh g under the current density -1 And excellent electrochemical performance is shown.
Example 2:
the difference between this embodiment and embodiment 1 is that, in embodiment 2, the mass ratio of the nano-silicon to the anhydrous stannous chloride is 1: 1. the rest preparation method and the steps are the same as the example 1, and the obtained nano silicon and stannic oxide composite anode material is marked as N-Si @ SnO 2 -1, from the material N-Si @ SnO 2 -1 preparing electrode material for testing.
Example 3:
the difference between this embodiment and embodiment 1 is that, in this embodiment 3, the mass ratio of the nano-silicon to the anhydrous stannous chloride is 3: 1. the rest preparation method and the steps are the same as the example 1, and the micron silicon and stannic oxide composite anode material marked as N-Si @ SnO is obtained 2 -3, from the material N-Si @ SnO 2 -3 preparing electrode material for testing.
Example 4:
the difference between this embodiment and embodiment 1 is that, in embodiment 4, micron silicon (particle size is 1-2 μm) is used, and the mass ratio of the micron silicon to the anhydrous stannous chloride is 3: 1. the rest preparation method and the steps are the same as the example 1, and the micron silicon and stannic oxide composite anode material marked as mu-Si @ SnO is obtained 2 -3, from the material μ -Si @ SnO 2 -3 preparing electrode material for testing.
Example 5:
the difference between this embodiment and embodiment 1 is that, in embodiment 5, micron silicon (particle size is 1-2 μm) is used, and the mass ratio of the micron silicon to the anhydrous stannous chloride is 1: 1. the rest preparation method and the steps are the same as the example 1, and the micron silicon and stannic oxide composite anode material marked as mu-Si @ SnO is obtained 2 -1, from the material μ -Si @ SnO 2 -1 preparing electrode material for testing.
Example 6:
the difference between this embodiment and embodiment 1 is that, in embodiment 6, micron silicon (particle size is 1-2 μm) is used, and the mass ratio of the micron silicon to the anhydrous stannous chloride is 2: 1. the rest preparation method and the steps are the same as the example 1, and the micron silicon and stannic oxide composite anode material marked as mu-Si @ SnO is obtained 2 -2, from the material μ -Si @ SnO 2 -2 preparing electrode material for testing.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.

Claims (10)

1. A silicon-tin nano material is characterized in that,
the silicon tin nano material comprises silicon particles and tin dioxide particles;
the tin dioxide particles are loaded on the surfaces of the silicon particles;
in the silicon tin nano material, the content ratio of silicon particles to tin dioxide is 2-3: 1.
2. The silicon-tin nanomaterial of claim 1,
the grain size of the silicon tin nano material is 1-2 mu m;
preferably, the silicon particles comprise nano-silicon and/or micro-silicon;
preferably, the particle size of the nano silicon is 50-100 nm;
preferably, the particle size of the micron silicon is 1-5 μm;
preferably, the particle size of the tin dioxide particles is 1-2 nm.
3. A method for preparing the silicon-tin nanomaterial according to any one of claims 1 to 2,
the method comprises the following steps:
and mixing, melting and calcining raw materials containing silicon powder and stannous chloride to obtain the silicon-tin nano material.
4. The production method according to claim 3,
the mass ratio of the silicon powder to the stannous chloride is 1-3: 1.
5. the production method according to claim 3,
the stannous chloride is anhydrous stannous chloride.
6. The production method according to claim 3,
the melting temperature is 280-300 ℃;
the melting time is 2-3 h.
7. The production method according to claim 3,
the calcining temperature is 280-300 ℃;
the calcining time is 2-3 h.
8. The production method according to claim 3,
the melting and calcining atmosphere is an inert gas atmosphere;
the inactive gas is selected from at least one of nitrogen, argon, helium or neon.
9. A negative electrode material for a lithium ion battery is characterized in that,
the negative electrode material for the lithium ion battery comprises the silicon-tin nano material of claim 1 or 2 or the silicon-tin nano material prepared by the preparation method of any one of claims 3 to 8.
10. The negative electrode material for a lithium ion battery according to claim 9,
the negative electrode material is 100mAg -1 The capacity is maintained at 2500mAh g under the current density -1 ；
At 1000mAg -1 The capacity is maintained at 1500mAhg under the current density -1 。
CN202210562953.1A 2022-05-23 2022-05-23 Silicon-tin nano material and preparation method and application thereof Withdrawn CN114843479A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116314833A (en) * 2023-05-25 2023-06-23 江苏时代新能源科技有限公司 Silicon-metal oxide composite material, method for producing same, secondary battery, and electricity-using device
CN117727915A (en) * 2024-02-07 2024-03-19 长沙矿冶研究院有限责任公司 Silicon-carbon composite material with micro silicon crystal size and preparation method and application thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116314833A (en) * 2023-05-25 2023-06-23 江苏时代新能源科技有限公司 Silicon-metal oxide composite material, method for producing same, secondary battery, and electricity-using device
CN116314833B (en) * 2023-05-25 2023-10-20 江苏时代新能源科技有限公司 Silicon-metal oxide composite material, method for producing same, secondary battery, and electricity-using device
CN117727915A (en) * 2024-02-07 2024-03-19 长沙矿冶研究院有限责任公司 Silicon-carbon composite material with micro silicon crystal size and preparation method and application thereof

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Application publication date: 20220802