CN115010137B - Method for rapidly preparing silicon nanowires by using cut waste silicon powder and application - Google Patents
Method for rapidly preparing silicon nanowires by using cut waste silicon powder and application Download PDFInfo
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 120
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- 239000002070 nanowire Substances 0.000 title claims abstract description 56
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- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
- C01B33/037—Purification
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a method for rapidly preparing silicon nanowires by using waste cut silicon powder, and belongs to the technical field of secondary resource utilization. The method is characterized in that crystalline silicon cutting waste silicon powder in the photovoltaic industry is used as a silicon source, graphene is used as a substrate, and a silicon nanowire is rapidly prepared on the graphene substrate through a high-temperature rapid thermal shock process. The preparation method comprises the following steps: (1) Mixing the cut waste silicon powder and graphene powder according to a certain proportion to prepare uniformly dispersed suspension; (2) carrying out suction filtration on the mixed suspension to prepare a filter membrane; (3) Heating the filter membrane in a reducing atmosphere to pre-reduce the functional groups in the graphene partially; (4) And (3) carrying out electro-thermal shock on the pre-reduced filter membrane to prepare the graphene-loaded silicon nanowire. When the film of the graphene loaded silicon nanowire is used for a lithium ion battery cathode, the film has high silicon content and good electrochemical cycling stability. The method prepares the cut waste silicon powder into the silicon nanowire by a rapid thermal shock method and is used for the lithium ion battery cathode material, the method is simple and green, the preparation process is rapid, and the high-value recycling of the cut waste silicon powder is easy to realize.
Description
Technical Field
The invention belongs to the technical field of secondary resource utilization, and discloses a method for rapidly preparing silicon nanowires by using cut waste silicon powder and application thereof.
Background
The photovoltaic industry can generate fine-granularity and high-purity cut waste silicon powder which is about 40% of the total mass of a silicon ingot in the cutting process of crystalline silicon wafers. The annual production of waste silicon powder in China has exceeded 10 ten thousand tons so far, and the waste silicon powder also increases sharply along with the increase of the installed quantity of crystalline silicon solar cells. Simple stacking, degradation treatment, or re-entry to the photovoltaic industry through complex purification procedures is its current state of treatment. The feature of fine particle size and high purity of the cut silicon waste powder is considered to be a low cost, reliable source of silicon for the production of nanostructured silicon.
In recent years, lithium ion power batteries in the new energy field are vigorously developed, and the requirement for high-energy-density anode materials is urgent. Silicon has the advantages of high theoretical specific capacity (3579 mAh/g), proper lithium intercalation/deintercalation voltage platform and the like as a negative electrode material, and is considered to be one of the highest potential high specific energy negative electrode materials of the next generation. However, silicon materials have large volume changes and poor electrical conductivity during charge and discharge processes, which limit commercial applications. Because of the special properties, the silicon nanowire has great potential application value in the aspects of nano electronic devices, optoelectronic devices, new energy sources and the like. In the field of new energy lithium ion power batteries, compared with a bulk material, the application of the silicon nanowire to a lithium battery anode material has the outstanding advantage that: the method has high tolerance to the electrode volume change in the circulation process, and can avoid the damage of the electrode structure to a greater extent; the specific surface area is large, which is beneficial to the effective contact between the electrolyte and the electrode and reduces the charge and discharge time; the electron transport and ion diffusion distance can be shortened, and the capacity and multiplying power of the battery are improved.
The preparation method of the silicon nanowire mainly comprises the following steps of firstly, a laser ablation method, wherein a metal catalyst or a mixture of silicon monoxide or silicon and silicon dioxide is used as a target material, and the prepared silicon nanowire contains catalyst metal, has long process time consumption and high equipment requirement and high energy consumption [ A.M.Morales, C.M.Lieber, A laser ablation method for the synthesis of crystalline semiconductor nanowires.science,1998,279:208-211]; secondly, chemical Vapor Deposition (CVD), CN 104103821 adopts a chemical vapor deposition method to prepare the silicon nanowire, and the method needs to use a catalyst and silane as silicon sources, and the preparation process is accompanied by toxic gas, and has complex process and long time consumption; thirdly, a fused salt electrolysis method, CN 102154659A discloses a method for preparing silicon nanowires by refining industrial silicon through fused salt electrolysis, a large amount of flux salt is needed during the preparation of the method, and the prepared nanowires mostly contain impurity metals, so that the electrolysis preparation process is long, difficult to control and high in energy consumption.
The invention develops a novel method, which uses micron-sized cutting waste silicon powder as a silicon source, and prepares the high-purity nanowire with adjustable diameter rapidly in a time of less than 1 second through electro-thermal shock. Compared with other preparation methods, the method does not need to use metal catalyst, expensive and toxic silicon raw materials, and the preparation process is simple, rapid (< 1 second) and low in energy consumption. In addition, the composite of the silicon nanowire and the carbon substrate can be realized in one step, and the graphene film loaded with the silicon nanowire can be obtained and can be directly used as a self-supporting electrode for the negative electrode of the lithium ion battery.
Disclosure of Invention
The invention provides a method for rapidly preparing silicon nanowires by using the waste cutting silicon powder, which is used for a lithium ion battery cathode material, shows excellent electrochemical performance and provides a new thought for the high-value utilization of the waste cutting silicon powder. The method comprises the following steps:
(1) Dispersing the dried cut waste silicon powder and graphene in a solvent according to a certain mass ratio to form suspensions A and B; uniformly mixing the suspension A and the suspension B to prepare a suspension C;
(2) Carrying out suction filtration on the suspension C to obtain filter membranes with different sizes and thicknesses, and drying to obtain a graphene film loaded with the cut waste silicon powder;
(3) Placing the film obtained in the step (2) in a reducing atmosphere high-temperature furnace, pre-reducing to remove part of functional groups in the graphene, cooling the graphene with the furnace to room temperature, and taking out a sample for later use;
(4) The film loaded with the cutting waste silicon powder after the pre-reduction in the step (3) is rapidly prepared into a silicon nanowire through an electro-thermal shock process;
further, the cutting waste silicon powder used in the step (1) is obtained by drying waste silicon mud generated in the process of cutting crystalline silicon in the photovoltaic industry, and is flaky micron-sized powder with the purity of more than 98.5%;
further, the graphene powder in the step (1) is single-layer and multi-layer graphene oxide prepared by a physical method or a chemical method;
further, the mass ratio of the cutting waste silicon powder to the graphene is 1: 5-5: 1, a step of;
further, the solvent is one or more of the following combinations of deionized water, ethanol, glycol, methanol, glycerol, isopropanol, N-butanol, N-N dimethylformamide and N-methylpyrrolidone;
further, the size and thickness of the filter membrane are controlled by the size of a container used for suction filtration and the addition amount of materials;
further, in the pre-reduction step, heating to 100-600 ℃ in a reducing atmosphere, wherein the heating rate is 1-5 ℃/min, and the heat preservation time is 1-3 hours, so as to remove part of functional groups in the graphene through pre-reduction;
further, the silicon nanowire is rapidly prepared by using electro-thermal shock, the temperature is 1500-2500 ℃, and the thermal shock process time is 100 milliseconds-1 second.
The beneficial effects of the invention are as follows: the waste silicon material generated in the process of cutting the crystalline silicon in the photovoltaic industry is used as a silicon source, and the high-added-value silicon nanowire which can be used for the negative electrode of the lithium ion battery is prepared by using the technology with short range, green, low energy consumption and high efficiency, so that the recycling utilization of solid wastes is realized; the invention uses the waste silicon powder as the silicon source to replace the traditional silicon source which is processed for the second time and is high in cost and toxic, and the silicon nanowire preparation process does not need to use a metal catalyst, so that the product purity is high; compared with the traditional silicon nanowire preparation technology, the silicon nanowire preparation technology by thermal shock has the advantages of simple preparation process, high efficiency and low energy consumption. In addition, the technology can realize the combination of the silicon nanowire and the graphene in one step, is directly used for the negative electrode of the lithium ion battery, avoids the use of a current collector, a conductive additive and an adhesive, and can obviously improve the quality energy density of the battery.
Drawings
Fig. 1 is an SEM image of cut waste silicon powder according to embodiment 1 of the present invention.
FIG. 2 is a graph showing the particle size distribution of the cut waste silicon powder according to embodiment 1 of the present invention.
Fig. 3 is a TEM photograph of a silicon nanowire prepared by thermal shock according to embodiment 1 of the present invention.
Fig. 4 is an SEM picture of a silicon nanowire-graphene (mass ratio 1:1) composite film according to embodiment 1 of the present invention.
Fig. 5 is a graph of charge-discharge cycle performance and coulombic efficiency of a silicon nanowire-graphene composite film according to embodiment 1 of the present invention.
FIG. 6 is an SEM image of silicon nanowires prepared at a mass ratio of waste silicon powder to graphene of (2:1) according to example 2 of the present invention.
FIG. 7 is an SEM image of silicon nanowires prepared at a mass ratio of waste silicon powder to graphene of 1:2 according to example 3 of the present invention.
FIG. 8 is an SEM image of silicon nanowires prepared at a mass ratio of waste silicon powder to graphene of 1:4 according to example 4 of the present invention.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials, unless otherwise specified, are commercially available.
Example 1
(1) Dispersing the dried micron-sized cutting waste silicon powder and graphene powder into 50ml of water solution according to a mass ratio of 1:1; (2) Mixing the suspension containing the waste silicon powder and graphene; (3) Vacuum filtering the mixed suspension after ultrasonic dispersion to prepare a filter membrane, wherein the vacuum degree is-0.1 MPa, and the diameter is 50mm; (4) Drying the suction-filtered graphene filter membrane loaded with the waste silicon powder to form a film; (5) Pre-reducing the dried filter membrane, removing partial functional groups in graphene, and removing the functional groups in hydrogen (H 2 10 percent of argon (Ar, 90 percent) mixed gas, wherein the temperature is 300 ℃, the heating rate is 3 ℃/min, the temperature is kept constant for 1 hour, and then the mixture is naturally cooled to room temperature for pre-reduction treatment; (6) And (3) rapidly preparing the silicon nanowires by electro-thermal shock of the pre-reduced filter membrane, wherein the temperature of the thermal shock process is 2500 ℃ and the time is 800 milliseconds.
Scanning electron microscopy (JSM-7800), transmission electron microscopy (JEM-2100F), laser particle size analyzer (Mastersizer 2000) were used to test the cut waste silicon powder, the prepared silicon nanowires, and the graphene composite film supporting the silicon nanowires under the above conditions. The test results are shown in figures 1-4 respectively; the diameter of the silicon nanowires is about 50nm.
The silicon nanowire-graphene composite film prepared in the example 1 is directly used for a lithium ion battery anode material, a metal lithium sheet is used as a counter electrode, celgard2325 is used as a diaphragm, and 1mol/L LiPF is used 6 (the solvent is a mixed solution of ethylene carbonate and dimethyl carbonate in a volume ratio of 1:1) as an electrolyte, and the CR2032 type button battery shell is assembled into a button battery in a glove box protected by argon gas for assembly. The charge and discharge test is carried out, the test program is 200mA/g, the voltage charge and discharge interval is 0.01-3V, and the charge and discharge cycle performance is shown in figure 5.
Example 2
(1) Dispersing the dried micron-sized cutting waste silicon powder and graphene powder into 50ml of water solution according to a mass ratio of 2:1; (2) Mixing the suspension containing the waste silicon powder and graphene; (3) Vacuum filtering the mixed suspension after ultrasonic dispersion to prepare a filter membrane, wherein the vacuum degree is-0.1 MPa, and the diameter is 50mm; (4) Drying the suction-filtered graphene filter membrane loaded with the waste silicon powder to form a film; (5) Pre-reducing the dried filter membrane, removing partial functional groups in graphene, and removing the functional groups in hydrogen (H 2 10 percent of argon (Ar, 90 percent) mixed gas, wherein the temperature is 100 ℃, the heating rate is 1 ℃/min, the temperature is kept constant for 3 hours, and then the mixture is naturally cooled to room temperature for pre-reduction treatment; (6) And (3) rapidly preparing the silicon nanowires by electro-thermal shock of the pre-reduced filter membrane, wherein the temperature of the thermal shock process is 2000 ℃ and the time is 500 milliseconds.
The silicon nanowires and graphene films carrying the nanowires prepared above were tested by a scanning electron microscope (JSM-7800) and a transmission electron microscope (JEM-2100F), and the diameters of the silicon nanowires were about 100nm, as shown in fig. 6.
Example 3
(1) Dispersing the dried micron-sized cutting waste silicon powder and graphene powder into 50ml of water solution according to a mass ratio of 1:2; (2) Mixing the suspension containing the waste silicon powder and graphene; (3) Vacuum filtering the mixed suspension after ultrasonic dispersion to prepare a filter membrane, wherein the vacuum degree is-0.1 MPa, and the diameter is 50mm; (4) Drying the suction-filtered graphene filter membrane loaded with the waste silicon powder to form a film; (5) Pre-reducing the dried filter membrane, removing partial functional groups in graphene, and removing the functional groups in hydrogen (H 2 10%) argon (Ar, 90%) mixIn the gas, the temperature is 600 ℃, the heating rate is 5 ℃/min, the temperature is kept constant for 1h, and then the gas is naturally cooled to room temperature for pre-reduction treatment; (6) And (3) rapidly preparing the silicon nanowires by electro-thermal shock of the pre-reduced filter membrane, wherein the temperature of the thermal shock process is 1500 ℃ below zero and the time is 100 milliseconds.
The silicon nanowires and graphene films carrying the nanowires prepared above were tested by a scanning electron microscope (JSM-7800) and a transmission electron microscope (JEM-2100F), and the diameter of the silicon nanowires was about 40nm, as shown in fig. 7.
Example 4
(1) Dispersing dried micron-sized cutting waste silicon powder and graphene powder into 50ml of water solution according to a mass ratio of 1:4; (2) Mixing the suspension containing the waste silicon powder and graphene; (3) Vacuum-filtering the mixed suspension after ultrasonic dispersion to prepare a filter membrane, wherein the vacuum degree is-0.1 MPa, and the diameter is 50mm; (4) Drying the suction-filtered graphene filter membrane loaded with the waste silicon powder to form a film; (5) Pre-reducing the dried filter membrane, removing partial functional groups in graphene, and removing the functional groups in hydrogen (H 2 5 percent of argon (Ar, 95 percent) mixed gas, wherein the temperature is 300 ℃, the heating rate is 3 ℃/min, and the temperature is kept constant for 1 hour and then naturally cooled to room temperature for pre-reduction treatment; (6) And (3) rapidly preparing the silicon nanowires by electro-thermal shock of the pre-reduced filter membrane, wherein the temperature of the thermal shock process is 2000 ℃ and the time is 500 milliseconds.
The silicon nanowires and graphene films carrying the nanowires prepared above were tested by a scanning electron microscope (JSM-7800) and a transmission electron microscope (JEM-2100F), and the diameters of the silicon nanowires were about 20nm, as shown in fig. 8.
In the description of the present specification, the descriptions of the terms "one implementation," "some implementations," "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is a further detailed description of the invention in connection with specific embodiments, and it is not intended that the invention be limited to such description. It will be apparent to those skilled in the art that several simple deductions or substitutions can be made without departing from the spirit of the invention.
Claims (7)
1. The method for rapidly preparing the silicon nanowire by using the cut waste silicon powder is characterized by comprising the following steps of:
(1) Dispersing the dried cut waste silicon powder and graphene in a solvent according to a certain mass ratio to form suspensions A and B; uniformly mixing the suspension A and the suspension B to prepare a suspension C;
(2) Carrying out suction filtration on the suspension C to obtain filter membranes with different sizes and thicknesses, and drying to obtain a graphene film loaded with the cut waste silicon powder;
(3) Placing the film obtained in the step (2) in a reducing atmosphere high-temperature furnace, pre-reducing to remove part of functional groups in the graphene, cooling the graphene with the furnace to room temperature, and taking out a sample for later use;
(4) And (3) rapidly preparing the graphene film carrying the silicon nanowires through the film after pre-reduction in the step (3) through an electro-thermal shock process, and rapidly preparing the silicon nanowires through the electro-thermal shock at the temperature of 1500-2500 ℃ for 100 milliseconds-1 second.
2. A method for rapidly preparing silicon nanowires from cut waste silicon powder as claimed in claim 1, wherein: the waste silicon powder used in the step (1) is obtained by drying waste silicon mud generated in the process of cutting crystalline silicon in the photovoltaic industry, and the waste silicon powder is flaky micron-sized powder with the purity of more than 98.5%.
3. A method for rapidly preparing silicon nanowires from cut waste silicon powder as claimed in claim 1, wherein: the graphene powder in the step (1) is single-layer and multi-layer graphene oxide prepared by a physical method or a chemical method.
4. A method for rapidly preparing silicon nanowires from cut waste silicon powder as claimed in claim 1, wherein: the mass ratio of the cutting waste silicon powder to the graphene is 1: 5-5: 1.
5. a method for rapidly preparing silicon nanowires from cut waste silicon powder as claimed in claim 1, wherein: the solvent in the step (1) is one or more of deionized water, ethanol, glycol, methanol, glycerol, isopropanol, N-butanol, N-N dimethylformamide and N-methylpyrrolidone.
6. A method for rapidly preparing silicon nanowires from cut waste silicon powder as claimed in claim 1, wherein: the size and thickness of the filter membrane in the step (2) are controlled by the size of a container used for suction filtration and the addition amount of materials.
7. A method for rapidly preparing silicon nanowires from cut waste silicon powder as claimed in claim 1, wherein: in the step (3), the pre-reduction is carried out in a reducing atmosphere, the temperature is heated to 100-600 ℃, the heating rate is 1-5 ℃/min, and the heat preservation time is 1-3 h, so that partial functional groups in the graphene are removed through the pre-reduction.
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| CN103872296A (en) * | 2012-12-10 | 2014-06-18 | 中国人民解放军63971部队 | Method for preparing lithium ion battery porous silicon composite cathode material by industrial silicon waste material |
| CN105612277A (en) * | 2013-10-07 | 2016-05-25 | Spi公司 | A method for mass production of silicon nanowires and/or nanobelts, and lithium batteries and anodes using the silicon nanowires and/or nanobelts |
| WO2019161288A1 (en) * | 2018-02-15 | 2019-08-22 | The Research Foundation For The State University Of New York | Silicon-carbon nanomaterials, method of making same, and uses of same |
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| CN103872296A (en) * | 2012-12-10 | 2014-06-18 | 中国人民解放军63971部队 | Method for preparing lithium ion battery porous silicon composite cathode material by industrial silicon waste material |
| CN105612277A (en) * | 2013-10-07 | 2016-05-25 | Spi公司 | A method for mass production of silicon nanowires and/or nanobelts, and lithium batteries and anodes using the silicon nanowires and/or nanobelts |
| WO2019161288A1 (en) * | 2018-02-15 | 2019-08-22 | The Research Foundation For The State University Of New York | Silicon-carbon nanomaterials, method of making same, and uses of same |
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