CN110336003B - Porous silicon-based composite material and preparation method and application thereof - Google Patents
Porous silicon-based composite material and preparation method and application thereof Download PDFInfo
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- CN110336003B CN110336003B CN201910573914.XA CN201910573914A CN110336003B CN 110336003 B CN110336003 B CN 110336003B CN 201910573914 A CN201910573914 A CN 201910573914A CN 110336003 B CN110336003 B CN 110336003B
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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
- 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
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- H—ELECTRICITY
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- 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
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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Abstract
The invention discloses a porous silicon-based composite material and preparation and application thereof. The porous silicon-based composite material is composed of a porous silicon network framework, and silicon nanoparticles and amorphous SiO supported on the porous silicon network frameworkxThe particle size of the porous silicon network skeleton is 2-50 μm, the pore diameter is 10-500 nm, the particle size of the silicon nanoparticles is 1-100 nm, and SiO is addedxThe particle diameter of the nano particles is 1-100 nm and 0<x is less than or equal to 2. The invention provides application of the porous silicon-based composite material as a lithium ion battery cathode material, and when the porous silicon-based composite material is applied to the lithium ion battery cathode material, the cycle stability of a silicon-based cathode can be obviously improved.
Description
Technical Field
The invention relates to the field of lithium ion battery cathode materials, in particular to a porous silicon-based composite material and a preparation method and application thereof.
Background
Emerging markets such as electric vehicles and plug-in hybrid vehicles have generated a tremendous demand for high energy density, long cycle life, and low cost lithium ion batteries. Graphite is the most commonly used negative electrode material for commercial lithium ion batteries due to its lower theoretical capacity (372mAh g)-1) And cannot meet the performance requirements of high energy density. Therefore, silicon has an extremely high theoretical capacity (4200mAh g)-1) And a relatively low charge-discharge potential (<0.5Vvs.Li/Li+) And the lithium ion battery has gained wide attention and is considered to be one of the most promising next-generation lithium ion battery cathode materials. However, the large volume change during lithium intercalation: (>300%) can lead to cracking, dusting, flaking off of the silicon material, and ultimately to capacity fade.
In order to overcome the problem of poor cycling stability of silicon-based negative electrodes, porous silicon materials are generally used to improve their lithium storage properties. Because of the multipleAbundant pore channels in the pore silicon structure can effectively relieve stress generated by volume expansion of silicon, so that the circulation stability is improved; moreover, the larger specific surface area is also beneficial to better infiltrating the active material by the electrolyte, and the diffusion distance of lithium ions is shortened, so that excellent rate performance is obtained. Many magnesiothermic reduction methods have been reported as a common preparation method of porous silicon, but the magnesiothermic reduction methods reported in the literature or patents generally have the problems of low yield, complicated method and the like, and need to use a strong corrosive acid solution such as hydrofluoric acid and the like, which has certain dangerousness. CN102259858A discloses a method for preparing porous silicon by magnesiothermic reduction, which uses oxide SiO of siliconx(x is 0.5-2) is taken as a raw material, a mixture of silicon and magnesium oxide is generated through a magnesiothermic reduction reaction, then the magnesium oxide is selectively dissolved by using acid, and finally the self-supporting porous silicon material is obtained, wherein a scanning electron microscope image shows that the product has a nano porous structure and uniform pore size distribution; and XRD diffraction spectrum analysis of the material shows that the product with the nano porous structure consists of cubic phase nano silicon crystals. Although the preparation method of the porous silicon reduces the cost and improves the yield, and the preparation method is simple in preparation process, environment-friendly, high in preparation efficiency and good in repeatability, the prepared porous silicon material is used as a lithium ion battery cathode material, and the cycle stability of the prepared porous silicon material still needs to be improved.
Disclosure of Invention
The first purpose of the invention is to provide a porous silicon-based composite material, and the porous silicon skeleton of the porous silicon-based composite material is loaded with silicon nano-particles and amorphous SiOx(0<x is less than or equal to 2) nano particles.
The second purpose of the invention is to provide a preparation method of the porous silicon-based composite material, which is environment-friendly, simple to operate and high in yield.
The third purpose of the invention is to provide the application of the porous silicon-based composite material as the negative electrode material of the lithium ion battery, and the cycle stability of the silicon-based negative electrode is greatly improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides aThe porous silicon-based composite material is composed of a porous silicon network skeleton, and silicon nanoparticles and amorphous SiO supported on the porous silicon network skeletonxThe particle size of the porous silicon network skeleton is 2-50 μm, the pore diameter is 10-500 nm, the particle size of the silicon nanoparticles is 1-100 nm, and SiO is addedxThe particle diameter of the nano particles is 1-100 nm and 0<x≤2。
In a second aspect, the invention provides a preparation method of a porous silicon-based composite material, which comprises the following steps:
1) mixing SiOy(0<y is less than or equal to 2), and uniformly mixing the metal powder reducing agent and the molten salt according to the molar ratio of 1: 0.1-5: 0.1-10 to obtain a mixture; the SiOyMiddle, 0<y is less than or equal to 2, and the metal powder reducing agent is magnesium powder or aluminum powder;
2) transferring the mixture obtained in the step 1) to a tubular furnace, heating to 400-1000 ℃ under the protection of inert atmosphere, reacting for 0.2-12 hours, and cooling to room temperature to obtain a reaction product;
3) and (3) placing the reaction product in an aqueous solution of 0.1-10 mol/L acid for etching to remove reaction byproducts, wherein the acid is any one or a mixture of any more of hydrochloric acid, sulfuric acid, nitric acid, acetic acid and oxalic acid, and centrifuging, washing and drying to obtain the porous silicon-based composite material.
In the present invention, the SiOyIs any one or a mixture of silicon monoxide, silicon dioxide and non-stoichiometric silicon oxide.
In the invention, the molten salt is preferably NaCl, KCl or MgCl2、CaCl2、BaCl2、AlCl3Any one or a mixture of several of them in any proportion.
In the present invention, the SiOyThe mixing molar ratio of the metal powder reducing agent to the molten salt is preferably 1: 0.5-5: 5-10, and most preferably 1:1: 10.
In the step 2), the reaction temperature is preferably 600-800 ℃, and the reaction time is 2-8 hours; the reaction temperature is most preferably 700 ℃ and the reaction time is 5 h.
In step 2) of the present invention, the inert atmosphere is preferably argon, nitrogen or a mixture of argon and nitrogen in any proportion.
In a third aspect, the invention provides an application of the porous silicon-based composite material as a negative electrode material of a lithium ion battery. When the porous silicon-based composite material is applied to a lithium ion battery cathode material, the cycle stability of a silicon-based cathode can be remarkably improved.
Compared with the prior art, the invention has the beneficial effects that:
the preparation method of the porous silicon-based composite material unexpectedly loads silicon nanoparticles and amorphous SiO on a porous silicon frameworkxThe nano particles not only have higher yield, but also can obviously improve the cycling stability of the silicon-based negative electrode when being used as a negative electrode material of a lithium ion battery, and have excellent rate performance.
Drawings
Fig. 1 is an XRD pattern of the porous silicon-based composite material in example 1.
FIG. 2 is a TEM image of the porous silicon-based composite material of example 1.
Fig. 3 is a graph of the cell cycle performance of the porous silicon-based composite material of example 1.
Fig. 4 is a battery rate performance graph of the porous silicon-based composite material of example 1.
Fig. 5 is a graph of the cell cycle performance of the porous silicon-based composite material of example 2.
Fig. 6 is a graph of the cell cycle performance of the porous silicon-based composite material of example 3.
Fig. 7 is a graph of cell cycle performance for the porous silicon-based composite material of comparative example 1.
Fig. 8 is an SEM image of the porous silicon material prepared in comparative example 2.
Fig. 9 is a graph showing the battery cycle performance of the porous silicon material prepared in comparative example 2.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples, but the scope of the present invention is not limited thereto:
example 1:
(1) preparation of porous silicon-based composite material
Mixing SiOy(y is approximately equal to 1), uniformly mixing the precursor, the metal powder Mg and the molten salt NaCl according to the molar ratio of 1:1: 10; transferring the mixture to a tubular furnace, heating to 700 ℃ under the protection of inert atmosphere, reacting for 5 hours, and cooling to room temperature to obtain a reaction product; and placing the reaction product in 1mol/L hydrochloric acid solution for etching to remove reaction byproducts, and centrifuging, washing and vacuum drying at 80 ℃ to obtain the porous silicon-based composite material.
(2) Preparation of electrode sheet
Mixing the obtained porous silicon-based composite material, acetylene black and CMC binder according to a weight ratio of 7:1.5:1.5, preparing slurry, coating the slurry on a copper foil current collector, and drying at 60 ℃ for 10 hours under a vacuum condition to obtain the electrode slice. Using a metal lithium sheet as a counter electrode and using 1M LiPF6EC/DEC (V)EC:VDEC1:1) solution as electrolyte, to assemble a button cell. And carrying out charge-discharge cycle tests on the assembled lithium ion battery at different current densities within a voltage range of 0.01-1.0V.
FIG. 1 is an XRD spectrum of the porous silicon-based composite material obtained in this example, from which it can be seen that the broad peak corresponds to amorphous SiOxThe crystalline silicon peaks correspond to the silicon standard cards. FIG. 2 is a TEM image of the porous silicon-based composite material obtained in this example, and it can be observed that a plurality of nanoparticles are supported on the network skeleton of the porous silicon, wherein the nanoparticles can be observed in the silicon nanoparticle crystal particles
Interplanar spacing of (A), amorphous SiOxNo lattice fringes were observed for the nanoparticles. FIGS. 3 and 4 are graphs of cell performance of the resulting porous silicon-based composite material in this example, showing excellent cycling stability and rate performance at 4Ag-1Can still maintain 958mAh g at 500 weeks-1The reversible capacity of (a).
Example 2:
mixing SiOy(y is approximately equal to 2) precursor, metal powder Al and molten salt AlCl3Uniformly mixing according to the molar ratio of 1:5: 8; transferring the mixture into a tubular furnace, heating to 650 ℃ under the protection of inert atmosphere, reacting for 3 hours, and cooling to room temperature to obtain a reaction product; and placing the reaction product in a 0.1mol/L sulfuric acid solution for etching to remove reaction byproducts, and centrifuging, washing and drying in vacuum at 100 ℃ to obtain the porous silicon-based composite material.
An electrode, an assembled battery, and a charge-discharge cycle test were prepared as in example 1.
Example 3:
mixing SiOy(y is approximately equal to 1.5) uniformly mixing the precursor, the metal powder Mg and the molten salt KCl according to the molar ratio of 1:2: 7; transferring the mixture to a tubular furnace, heating to 500 ℃ under the protection of inert atmosphere, reacting for 3 hours, and cooling to room temperature to obtain a reaction product; and placing the reaction product in a 2mol/L nitric acid solution for etching to remove reaction byproducts, and centrifuging, washing and vacuum drying at 90 ℃ to obtain the porous silicon-based composite material.
An electrode, an assembled battery, and a charge-discharge cycle test were prepared as in example 1.
Comparative example 1:
mixing SiOy(y is approximately equal to 0.7) uniformly mixing the precursor and the metal powder Mg according to the molar ratio of 1: 0.1; transferring the mixture to a tubular furnace, heating to 800 ℃ under the protection of inert atmosphere, reacting for 0.2 hour, and cooling to room temperature to obtain a reaction product; and placing the reaction product in 10mol/L acetic acid solution for etching to remove reaction byproducts, and centrifuging, washing and vacuum drying at 90 ℃ to obtain the porous silicon-based composite material.
An electrode, an assembled battery, and a charge-discharge cycle test were prepared as in example 1.
Comparative example 2
Porous silicon was prepared according to CN102259858A example 1:
(1) SiO powder and magnesium powder are mixed according to a molar ratio of 1:1, uniformly mixing under the protection of argon, putting the mixture into a tubular atmosphere furnace, heating the mixture to 500 ℃ in argon flow, reacting the mixture for 6 hours at constant temperature, and naturally cooling the mixture to room temperature;
(2) and (3) placing the obtained product in hydrochloric acid with the concentration of 0.1mol/L for fully soaking for 24 hours, removing magnesium oxide, filtering to obtain a solid product, fully cleaning by deionized water, fully cleaning by absolute ethyl alcohol, and drying to obtain porous silicon powder.
An electrode, an assembled battery, and a charge-discharge cycle test were prepared as in example 1.
Fig. 8 is an SEM image of the porous silicon material prepared in this comparative example, and it can be found that the sample is a porous silicon network skeleton, and the surface thereof has no nano-particle loading. Fig. 9 is a graph showing the cell performance of the porous silicon material prepared in this comparative example, and it can be found that the capacity fade is fast.
The foregoing is a detailed description of the present invention with reference to preferred embodiments, but it should not be construed that the present invention is limited to the embodiments. It will be apparent to those skilled in the art to which the invention pertains that numerous modifications and alterations can be made without departing from the spirit of the invention, and such modifications and alterations are intended to be included within the scope of the invention as defined in the appended claims.
Claims (9)
1. A porous silicon-based composite material is prepared from a porous silicon network skeleton, and silicon nanoparticles and amorphous SiO supported on the skeletonxThe particle size of the porous silicon network skeleton is 2-50 μm, the pore diameter is 10-500 nm, the particle size of the silicon nanoparticles is 1-100 nm, and SiO is addedxThe particle diameter of the nano particles is 1-100 nm and 0<x is less than or equal to 2; the preparation method comprises the following steps:
1) mixing SiOyUniformly mixing the metal powder reducing agent and the molten salt according to a molar ratio of 1: 0.1-5: 0.1-10 to obtain a mixture; the SiOyMiddle, 0<y is less than or equal to 2, and the metal powder reducing agent is magnesium powder or aluminum powder;
2) transferring the mixture obtained in the step 1) to a tubular furnace, heating to 400-1000 ℃ under the protection of inert atmosphere, reacting for 0.2-12 hours, and cooling to room temperature to obtain a reaction product;
3) and (3) placing the reaction product in an aqueous solution of 0.1-10 mol/L acid for etching to remove reaction byproducts, wherein the acid is any one or a mixture of any more of hydrochloric acid, sulfuric acid, nitric acid, acetic acid and oxalic acid, and centrifuging, washing and drying to obtain the porous silicon-based composite material.
2. The method of claim 1, wherein: the SiOyIs any one or a mixture of silicon monoxide, silicon dioxide and non-stoichiometric silicon oxide.
3. The method of claim 1, wherein: the molten salt is NaCl, KCl and MgCl2、CaCl2、BaCl2、AlCl3Any one or a mixture of several of them in any proportion.
4. The method according to any one of claims 1 to 3, wherein: the SiOyAnd the mixing molar ratio of the metal powder reducing agent to the molten salt is 1: 0.5-5: 5-10.
5. The method of claim 4, wherein: the SiOyThe mixing molar ratio of the metal powder reducing agent to the molten salt is 1:1: 10.
6. The method according to any one of claims 1 to 3, wherein: in the step 2), the reaction temperature is 600-800 ℃, and the reaction time is 2-8 hours.
7. The method of claim 6, wherein: in the step 2), the reaction temperature is 700 ℃, and the reaction time is 5 h.
8. The method according to any one of claims 1 to 3, wherein: in the step 2), the inert atmosphere is argon, nitrogen or a mixed gas of argon and nitrogen in any proportion.
9. The porous silicon-based composite material prepared by the preparation method according to claim 1 is applied as a lithium ion battery negative electrode material.
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| CN111082000A (en) * | 2019-11-29 | 2020-04-28 | 湖北万润新能源科技发展有限公司 | Preparation method for optimizing SiOx @ C performance by using pore-forming agent |
| CN112366294B (en) * | 2020-07-31 | 2022-02-15 | 万向一二三股份公司 | Graphite/silicon/carbon composite negative electrode material and preparation method thereof |
| CN113800523B (en) * | 2021-09-09 | 2023-05-16 | 哈尔滨工业大学 | Layered porous silicon material and preparation method and application thereof |
| CN113793929B (en) * | 2021-09-16 | 2024-03-01 | 金川集团股份有限公司 | Porous Si/SiO x Preparation and application of composite material |
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| CN106129345A (en) * | 2016-06-17 | 2016-11-16 | 中国科学院宁波材料技术与工程研究所 | Multilayered structure material that a kind of silicon dioxide microsphere is embedded in continuous poriferous silicon matrix and preparation method thereof |
| CN108336342B (en) * | 2018-02-28 | 2020-10-13 | 宁波富理电池材料科技有限公司 | Si/SiOx/C composite negative electrode material, preparation method thereof and lithium ion battery |
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