CN107093738B - Preparation method of nano silicon-based material - Google Patents
Preparation method of nano silicon-based material Download PDFInfo
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- CN107093738B CN107093738B CN201710271252.1A CN201710271252A CN107093738B CN 107093738 B CN107093738 B CN 107093738B CN 201710271252 A CN201710271252 A CN 201710271252A CN 107093738 B CN107093738 B CN 107093738B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- 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
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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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- 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 field of energy storage research, and particularly relates to a preparation method of a nano silicon-based material, which mainly comprises (1) alloy preparation- (2) crushing- (3) de-intercalation-repeated (1) - (3) for multiple times or (1) alloy preparation- (2) de-intercalation- (3) crushing-repeated (1) - (3) for multiple times; through the alloy preparation process, the volume of the silicon-based material is expanded, cracks are formed inside the particles, and the subsequent crushing process is facilitated to carry out particle crushing; the non-silicon-based components in the alloy can be removed in the de-intercalation process to obtain a nano silicon-based material; repeated treatment can destroy the structure of the silicon-based particles for many times, so that the prepared product has smaller size.
Description
Technical Field
The invention belongs to the field of energy storage research, and particularly relates to a preparation method of a nano silicon-based material.
Background
Since the birth of the lithium ion battery, the lithium ion battery brings revolutionary changes to the field of energy storage due to the advantages of large specific energy, high working voltage, small self-discharge rate, small volume, light weight and the like, and is widely applied to various portable electronic devices and electric automobiles. However, with the improvement of living standard of people, higher user experience puts higher requirements on the lithium ion battery: lighter weight, longer service life, etc. In order to solve the above problems, it is necessary to find a new electrode material having more excellent properties.
The current commercialized lithium ion battery cathode material is mainly graphite, but the theoretical capacity of the lithium ion battery cathode material is only 372mAh g-1The urgent needs of users cannot be met. Therefore, the development of a negative electrode material with higher specific capacity is imminent. Silicon materials have been attracting attention as negative electrode materials for lithium ion batteries. The theoretical capacity is 4200mAh g-1More than 10 times the capacity of the commercial graphite. And the lithium-insertion-capacity anode material has the advantages of low lithium insertion potential, low atomic weight, high energy density, low price, environmental friendliness and the like, and becomes one of the optimal choices of a new-generation high-capacity anode material. However, the silicon material has poor conductivity, and the volume expansion is large in the charging and discharging process, so that the material structure is easy to damage and mechanically crush, and the cycle performance of the material is quickly attenuated, and the wider application of the material is limited.
In order to solve the problems, the prior art mainly comprises the steps of nano-granulating silicon particles, and then re-pelletizing to obtain micron-sized secondary particles of silicon-based materials, so as to solve the problems of mechanical crushing of the silicon-based materials in the charging and discharging processes of the materials and the like. The existing silicon particle nano technology is mainly obtained by directly and mechanically crushing silicon-based materials with large particle sizes. However, silicon-based material atoms are tightly combined, the nano-grade crushing difficulty is high, the requirements on equipment are high, and the energy consumption is high, so that the prepared nano silicon-based material is high in price, and the wide application of the silicon-based negative electrode material is limited.
In view of the above, there is a need to provide a new technical solution for controllably preparing nanoscale silicon-based materials in large quantities at low cost.
Disclosure of Invention
The invention aims to: aiming at the defects of the prior art, the method for preparing the nano silicon-based material is provided, and mainly comprises (1) alloy preparation- (2) crushing- (3) de-intercalation-repeated for multiple times of (1), (2) and (3) or (1), (3) and (2). Through the alloy preparation process, the volume of the silicon-based material is expanded, cracks are formed inside the particles, and the subsequent crushing process is facilitated to carry out particle crushing; the non-silicon-based component in the alloy can be removed in the de-intercalation process so as to obtain a nano silicon-based material; repeated treatment for many times can destroy the structure of the silicon-based particle material for many times, so that the final product has smaller size. In addition, the method has universality, and can be used for preparing lithium ion battery negative electrode nano-particle materials with large volume expansion in all charging processes, such as nano aluminum particles, nano tin particles and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a nano silicon-based material mainly comprises the following steps: step 1, preparing an alloy: selecting silicon-based particles with the particle size of D0 as a reactant, and embedding new elements into the silicon-based particles to obtain silicon-based alloy particles with expanded volume; step 2, crushing: applying external force to crush the alloy material obtained in the step 1 to obtain alloy particles with the particle size of D1'; step 3, de-intercalation: removing non-silicon-based components in the alloy particles with the particle size of D1' to obtain silicon-based materials with the particle size of D1; and 4, repeating the operation for n times according to the sequence of the step 1-2-3 or the step 1-3-2, and finally obtaining the nano silicon-based material with the particle size Dn, wherein n is more than or equal to 2.
As an improvement of the preparation method, in the step 1, the particle size D0 of the large-size silicon particles is more than or equal to 1 μm, and the silicon particles comprise at least one of simple substance silicon, silicon oxide and silicon-based composite material.
As an improvement of the preparation method of the invention, in step 1, the new element comprises at least one of lithium, sodium, aluminum and magnesium, and the intercalation mode is carried out by adopting an electrochemical reaction intercalation method.
As a further improvement of the preparation method of the invention, the electrochemical reaction intercalation method comprises the following processes: blending the silicon-based particles with a power source substance to form an electronic channel, then adding electrolyte to form an ion channel, and carrying out an electrical reaction to obtain silicon-based alloy particles; or preparing the silicon-based particles into electrodes, using the electrodes made of power source substances as counter electrodes, adding electrolyte to form ion channels, connecting an external circuit to form electronic channels, and carrying out electrochemical reaction to obtain the silicon-based alloy particles.
Further, a potential difference exists between the power source substance and the silicon-based particles, and when an electronic channel and an ion channel are formed simultaneously, ions in the power source substance are extracted and automatically embedded into the silicon-based particles; or the power source substance is capable of providing ions capable of reacting with the silicon-based particles to form silicon-based alloy particles; the electrolyte can conduct ions extracted from the power source material.
Further, the power source substance includes at least one of a lithium-rich substance, a positive electrode material capable of providing ions, and a metal substance as an electrode material; the electrolyte comprises a solute and a solvent, the solute comprises ions removed from the power source substance, and the concentration of the solute is 0.1-1.5 mol/L.
Preferably, the lithium-rich substance comprises at least one of a pre-embedded lithium negative electrode material and a lithium-rich positive electrode material, the metal substance serving as the electrode material comprises at least one of metal lithium, metal sodium, metal potassium, metal magnesium, metal aluminum and metal zinc, and the electrolyte is at least one of a lithium ion battery electrolyte, a lithium sulfur battery electrolyte, a sodium ion battery electrolyte, an aluminum ion battery electrolyte, a zinc ion battery electrolyte, a magnesium ion battery electrolyte and a lead-acid battery electrolyte.
As an improvement of the preparation method of the invention, in the step 2, the external force is applied in a manner of at least one of ball milling, high-speed shearing, high-pressure impact and high-speed impact.
As an improvement of the preparation method of the invention, in the step 3, the non-silicon component removing method comprises the steps of preparing the alloy particles obtained in the step 2 into electrodes, assembling the electrodes with electrolyte and a counter electrode to form a primary battery, charging, and removing the non-silicon component in the alloy to obtain the nano silicon-based material particles.
Furthermore, the electrode prepared from the alloy particles contains a conductive agent, the electrolyte can conduct ions extracted from the alloy particles, the counter electrode can receive the ions extracted from the alloy particles, and the electrode made from the alloy particles is electrically insulated from the counter electrode.
As an improvement of the preparation method of the invention, in the step 3, the non-silicon component is removed by adding an active reaction substance to react with the alloy particles obtained in the step 2, and ions embedded in the silicon-based particles in the step 1 are removed to obtain the nano silicon-based material particles.
Preferably, the reactive species comprise at least one of water, an acid, a base, an organic solvent.
The invention has the advantages that:
1. through multiple embedding-de-embedding processes, the volume of the silicon-based material is expanded and contracted for multiple times, the internal structure of the silicon-based material is damaged for multiple times, and therefore the nano silicon particles with smaller granularity are easily prepared.
2. When the repeated operations of intercalation-deintercalation-crushing are used, the crushing stage is already a pure silicon-based material, the reactivity of the material is lower, the environmental conditions required by the crushing are lower, and the crushing operation is more facilitated.
3. The alloy is formed in an electrochemical mode, so that the large-size silicon-based particles expand in volume, cracks appear in the particles, and the subsequent crushing process is facilitated. Meanwhile, the reaction depth, namely the volume expansion degree, of the silicon-based material can be controlled according to the mass ratio between the large-size silicon-based particles and the power source.
4. The reaction speed between the large-size silicon-based particles and the power source object is controlled by controlling the charging current, the concentration of solute in the electrolyte, the reaction temperature between the large-size silicon-based particles and the power source object and the pressure applied during reaction. When the reaction speed is fast, the volume of the large-size silicon-based particles is rapidly expanded, the stress release is lower, cracks are easier to form in the particles, and the follow-up crushing work is more facilitated.
5. In the whole preparation process, impurities of a non-battery system are not introduced, and the low impurity content of the prepared nano silicon-based material is ensured.
6. The method is simple and easy to implement, low in preparation cost and easy for large-scale production.
Detailed Description
The present invention and its advantageous effects will be described in detail below with reference to specific embodiments, but the embodiments of the present invention are not limited thereto.
Comparative example
Selecting simple substance silicon with the grain diameter of 50 mu m, and carrying out high-pressure homogenization (namely, carrying out high-speed impact on the grains) treatment to prepare crushed silicon grains.
Example 1
Step 1, preparing an alloy: selecting simple substance silicon with the particle size of 50 mu m, metal lithium and 1mol/L lithium hexafluorophosphate as electrolyte, uniformly mixing the electrolyte of the lithium ion battery, applying the pressure of 1MPa to the mixture, and then fully reacting at 25 ℃ to ensure that lithium ions are embedded into the simple substance silicon particles to obtain silicon-based alloy particles with the particle size of D1'.
Step 2, crushing: and (2) in an inert atmosphere, carrying out high-pressure homogenization (namely, carrying out high-speed impact on the particles) on the silicon-based alloy particles obtained in the step (1) to obtain the crushed silicon-based alloy particles.
Step 3, de-intercalation: and (3) uniformly mixing the crushed silicon-based alloy particles obtained in the step (2) with a conductive agent to prepare an electrode, assembling the electrode with a lithium ion battery electrolyte taking lithium hexafluorophosphate as an electrolyte and a copper current collector as a counter electrode to obtain a primary battery, and then charging to remove lithium ions in the silicon-based alloy particles.
And 4, repeating the process of the step 1 to the process of the step 3 once, and performing embedding-crushing-de-embedding treatment on the silicon-based material twice to obtain the nano silicon-based material particles.
Example 2
The difference from embodiment 1 is that this embodiment includes the following steps: and 4, repeating the processes of the steps 1 to 3 twice, and carrying out three times of embedding-crushing-de-embedding treatment on the silicon-based material to obtain the nano silicon-based material particles.
The rest is the same as that of embodiment 1 and will not be repeated here.
Example 3
The difference from the embodiment 1 is that the order of the step 2 and the step 3 is exchanged, and the rest is the same as that of the embodiment 1, and is not repeated here.
Example 4
The difference from embodiment 1 is that this embodiment includes the following steps: in the step 1, simple substance silicon with the particle diameter of 50 mu m, metal lithium and lithium hexafluorophosphate with the particle diameter of 1mol/L are selected as electrolyte of the lithium ion battery, the mixture is uniformly mixed, the pressure of 1MPa is applied to the mixture, and then the mixture is fully reacted at the temperature of 0 ℃, so that lithium ions are embedded into the simple substance silicon particles, and the silicon-based alloy particles are obtained.
The rest is the same as that of embodiment 1 and will not be repeated here.
Example 5
The difference from embodiment 1 is that this embodiment includes the following steps: in the step 1, simple substance silicon with the particle diameter of 50 mu m, metal lithium and lithium hexafluorophosphate with the particle diameter of 1mol/L are selected as electrolyte of the lithium ion battery, the mixture is uniformly mixed, the pressure of 1MPa is applied to the mixture, and then the mixture is fully reacted at the temperature of 60 ℃, so that lithium ions are embedded into the simple substance silicon particles, and the silicon-based alloy particles are obtained.
The rest is the same as that of embodiment 1 and will not be repeated here.
Example 6
The difference from embodiment 1 is that this embodiment includes the following steps: in the step 1, simple substance silicon with the particle diameter of 50 mu m, metal lithium and lithium hexafluorophosphate with the particle diameter of 1mol/L are selected as electrolyte of the lithium ion battery, the mixture is uniformly mixed, the pressure of 1MPa is applied to the mixture, and then the mixture is fully reacted at the temperature of 90 ℃, so that lithium ions are embedded into the simple substance silicon particles, and the silicon-based alloy particles are obtained.
The rest is the same as that of embodiment 1 and will not be repeated here.
Example 7
The difference from embodiment 1 is that this embodiment includes the following steps: in the step 1, simple substance silicon with the particle diameter of 50 mu m, metal lithium and lithium hexafluorophosphate with the particle diameter of 1mol/L are selected as electrolyte of the lithium ion battery, the mixture is uniformly mixed, the pressure of 1MPa is applied to the mixture, and then the mixture is fully reacted at 120 ℃ to ensure that lithium ions are embedded into the simple substance silicon particles, so that silicon-based alloy particles are obtained.
The rest is the same as that of embodiment 1 and will not be repeated here.
Example 8
The difference from embodiment 1 is that this embodiment includes the following steps: in the step 1, elementary silicon with the particle diameter of 50 microns, metal lithium and lithium hexafluorophosphate with the particle diameter of 0.1mol/L are selected as electrolyte of the lithium ion battery, the electrolyte is uniformly mixed, the pressure of 1MPa is applied to the mixture, and then the mixture is fully reacted at the temperature of 90 ℃, so that lithium ions are embedded into the elementary silicon particles, and the silicon-based alloy particles are obtained.
The rest is the same as that of embodiment 1 and will not be repeated here.
Example 9
The difference from embodiment 1 is that this embodiment includes the following steps: in the step 1, elementary silicon with the particle diameter of 50 microns, metal lithium and lithium hexafluorophosphate with the particle diameter of 1.2mol/L are selected as electrolyte of the lithium ion battery, the electrolyte is uniformly mixed, the pressure of 1MPa is applied to the mixture, and then the mixture is fully reacted at the temperature of 90 ℃, so that lithium ions are embedded into the elementary silicon particles, and the silicon-based alloy particles are obtained.
The rest is the same as that of embodiment 1 and will not be repeated here.
Example 10
The difference from embodiment 1 is that this embodiment includes the following steps: in the step 1, simple substance silicon with the particle diameter of 50 mu m, metal lithium and lithium hexafluorophosphate with the particle diameter of 1mol/L are selected as electrolyte of the lithium ion battery, the mixture is uniformly mixed, the pressure of 0.1MPa is applied to the mixture, and then the mixture is fully reacted at the temperature of 90 ℃ to ensure that lithium ions are embedded into the simple substance silicon particles, so that the silicon-based alloy particles are obtained.
The rest is the same as that of embodiment 1 and will not be repeated here.
Example 11
The difference from embodiment 1 is that this embodiment includes the following steps: in the step 1, simple substance silicon with the particle diameter of 50 mu m, metal lithium and lithium hexafluorophosphate with the particle diameter of 1mol/L are selected as electrolyte of the lithium ion battery, the mixture is uniformly mixed, the pressure of 10MPa is applied to the mixture, and then the mixture is fully reacted at the temperature of 90 ℃, so that lithium ions are embedded into the simple substance silicon particles, and the silicon-based alloy particles are obtained.
The rest is the same as that of embodiment 1 and will not be repeated here.
Example 12
The difference from embodiment 1 is that this embodiment includes the following steps: in the step 1, simple substance silicon with the particle diameter of 50 mu m, metal lithium and lithium hexafluorophosphate with the particle diameter of 1mol/L are selected as electrolyte of the lithium ion battery, the mixture is uniformly mixed, the pressure of 50MPa is applied to the mixture, and then the mixture is fully reacted at the temperature of 90 ℃, so that lithium ions are embedded into the simple substance silicon particles, and the silicon-based alloy particles are obtained.
The rest is the same as that of embodiment 1 and will not be repeated here.
Example 13
The difference from embodiment 1 is that this embodiment includes the following steps:
step 1, preparing an alloy, namely selecting simple substance silicon with the particle size of 50 mu m and a conductive agent (SuperP) to be uniformly mixed to prepare a silicon-based electrode, assembling a primary battery by taking a metal lithium sheet as a counter electrode and a PP film as an isolating film, applying 10MPa of pressure on the surface of the primary battery by taking 1.2mol/L of lithium hexafluorophosphate as electrolyte of a lithium ion battery electrolyte, and then applying 1C current to an external circuit for charging at 80 ℃ so that lithium ions are embedded into simple substance silicon particles from one side of the metal lithium through the isolating film to obtain silicon-based alloy particles.
The rest is the same as that of embodiment 1 and will not be repeated here.
Example 14
The difference from the example 13 is that the external circuit in the step 1 applies a current of 0.01C for charging, and the rest is the same as the example 13 and is not repeated here.
Example 15
The difference from the embodiment 13 is that the external circuit applies 0.1C current for charging in the step 1, and the rest is the same as the embodiment 13, and is not repeated here.
Example 16
The difference from the embodiment 13 is that the external circuit applies a current of 5C for charging in the step 1, and the rest is the same as the embodiment 13 and is not repeated here.
Example 17
The difference from the embodiment 13 is that the external circuit applies a current of 20C for charging in the step 1, and the rest is the same as the embodiment 13 and is not repeated here.
Example 18
The difference from the embodiment 13 is that the external circuit in the step 1 applies a current of 100C for charging, and the rest is the same as the embodiment 13 and is not repeated here.
Example 19
Step 1, preparing an alloy: selecting silicon oxide with the particle size of 80 mu m and a conductive agent (carbon nano tube) to be uniformly mixed to prepare a silicon-based electrode, preparing a counter electrode by taking lithium iron phosphate as an active substance, assembling a PE film as an isolating film to form a primary battery, applying 1mol/L lithium hexafluorophosphate as a lithium ion battery electrolyte of the electrolyte to the surface of the primary battery under the pressure of 1MPa, and then applying 1C current to an external circuit to charge at 25 ℃ so that lithium ions are embedded into silicon oxide particles from one side of the lithium iron phosphate through the isolating film to obtain silicon-based alloy particles.
Step 2, crushing: and (3) in an inert atmosphere, carrying out mechanical ball milling treatment on the silicon-based alloy particles obtained in the step (1) to obtain the crushed silicon-based alloy particles.
Step 3, de-intercalation: and (3) uniformly mixing the crushed silicon-based alloy particles obtained in the step (2) with a conductive agent to prepare an electrode, assembling the electrode with a lithium ion battery electrolyte taking lithium hexafluorophosphate as an electrolyte and a lithium belt as a current collector as a counter electrode to obtain a primary battery, and then charging to remove lithium ions in the silicon-based alloy particles.
And 4, repeating the process of the step 1 to the process of the step 3 once, and performing embedding-crushing-de-embedding treatment on the silicon-based material twice to obtain the nano silicon-based material particles.
Example 20
The difference from embodiment 19 is that this embodiment includes the following steps: step 3, de-intercalation: and (3) adding deionized water into the crushed silicon-based alloy particles obtained in the step (2) to enable the silicon-based alloy to react with the water, and removing lithium ions in the silicon-based alloy particles.
The rest is the same as that of example 19 and will not be repeated here.
Example 21
Step 1, preparing an alloy: selecting a silicon-carbon composite material with the particle diameter of 1 mu m, magnesium powder, 1.5mol/L magnesium sulfate aqueous solution as electrolyte (containing 1 wt% of ethylene sulfate additive) and conductive carbon black, uniformly mixing, applying the pressure of 1MPa to the mixture, and then fully reacting at 25 ℃ to ensure that magnesium ions in the magnesium powder are embedded into the silicon-carbon composite material to obtain the silicon-based alloy particles.
Step 2, de-intercalation: and (3) uniformly mixing the crushed silicon-based alloy particles obtained in the step (2) with a conductive agent to prepare an electrode, assembling the electrode with an electrolyte (containing 1 wt% of an ethylene sulfate additive) which is a magnesium sulfate aqueous solution and a magnesium tape which is a current collector as a counter electrode to obtain a primary battery, then charging, and removing magnesium ions in the silicon-based alloy particles to obtain the silicon-based particles after de-intercalation.
And step 3, crushing: and (3) in an inert atmosphere, carrying out mechanical ball milling treatment on the silicon-based particles obtained in the step (2) to obtain the crushed silicon-based particles.
And 4, repeating the process of the step 1 to the process of the step 3 once, and performing embedding-de-embedding-crushing treatment on the silicon-carbon composite material twice to obtain the silicon-based nano material particles.
Example 22
The difference from embodiment 21 is that, in step 2, 1mol/L of dilute sulfuric acid solution is added to the silicon-based alloy particles obtained in step 1, so that the silicon-based alloy reacts with dilute hydrochloric acid, and magnesium ions in the silicon-based alloy particles are removed, thereby obtaining the nano silicon-based particles.
The rest is the same as that of embodiment 21, and is not repeated here.
Example 23
Step 1, preparing an alloy: selecting a silicon-carbon composite material with the particle diameter of 1 mu m to prepare a silicon-based electrode, assembling a primary battery by taking a metal aluminum sheet as a counter electrode and a PE film as an isolating film, taking 1.5mol/L aluminum chloride-triethylamine hydrochloride ionic liquid as electrolyte, applying the pressure of 1MPa to the surface of the primary battery, and then applying 1C current to an external circuit at 25 ℃ for charging so that aluminum ions are embedded into the silicon-carbon composite material from one side of metal aluminum through the isolating film to obtain silicon-based alloy particles.
Step 2, crushing: and (3) in an inert atmosphere, carrying out mechanical ball milling treatment on the silicon-based alloy particles obtained in the step (1) to obtain the crushed silicon-based alloy particles.
Step 3, preparing nano silicon-based particles: and (3) uniformly mixing the crushed silicon-based alloy particles obtained in the step (2) with a conductive agent to prepare an electrode, assembling the electrode with an aluminum chloride-triethylamine hydrochloride ionic liquid serving as an electrolyte and an aluminum foil serving as a current collector serving as a counter electrode to obtain a primary battery, then charging, and removing aluminum ions in the silicon-based alloy particles to obtain the silicon-based particles after de-intercalation.
And 4, repeating the process of the step 1 to the process of the step 3 once, and performing embedding-crushing-de-embedding treatment on the silicon-carbon composite material twice to obtain the silicon-based nano material particles.
Example 24
The difference from embodiment 23 is that this embodiment includes the following steps: and 3, adding 1mol/L dilute hydrochloric acid solution into the crushed silicon-based alloy particles obtained in the step 2, so that the silicon-based alloy reacts with the dilute hydrochloric acid, and removing aluminum ions in the silicon-based alloy particles to obtain the nano silicon-based particles.
The rest is the same as that of example 23 and will not be repeated here.
And (3) particle size testing: the particle diameters of the nano silicon-based materials prepared in the comparative examples and examples were measured using a laser particle sizer, and the value of D50 was recorded, as shown in table 1.
TABLE 1 particle size of the nano-sized silicon-based materials prepared in the different comparative examples and examples (D50)
As can be seen from Table 1, the preparation method of the nano silicon-based material prepared by the invention can prepare the nano silicon-based material with smaller granularity. Specifically, the nano silicon-based material with smaller particle size can be obtained after multiple de-intercalation and crushing treatments. The preparation method has universality and is suitable for preparation of various nano silicon-based particle materials, which can be obtained from the examples 21 to 24.
Variations and modifications to the above-described embodiments may become apparent to those skilled in the art from the disclosure and teachings of the above description. Therefore, the present invention is not limited to the above-mentioned embodiments, and any obvious improvement, replacement or modification made by those skilled in the art based on the present invention is within the protection scope of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (9)
1. A preparation method of a nano silicon-based material mainly comprises the following steps:
step 1, preparing an alloy: selecting silicon-based particles with the particle size of D0 as a reactant, and embedding new elements into the silicon-based particles to obtain silicon-based alloy particles with expanded volume;
step 2, crushing: applying external force to crush the alloy material obtained in the step 1 to obtain alloy particles with the particle size of D1';
step 3, de-intercalation: removing non-silicon-based components in the alloy particles with the particle size of D1' to obtain silicon-based materials with the particle size of D1;
step 4, repeating the operation for n times according to the sequence of the step 1-2-3 or the step 1-3-2, and finally obtaining the nano silicon-based material with the particle size Dn, wherein n is more than or equal to 2;
the embedding mode in the step 1 is carried out by adopting an electrochemical reaction embedding method; the electrochemical reaction intercalation method comprises the following processes: blending the silicon-based particles with a power source substance to form an electronic channel, then adding electrolyte to form an ion channel, and carrying out an electrical reaction to obtain silicon-based alloy particles; or preparing the silicon-based particles into electrodes, using the electrodes made of power source substances as counter electrodes, adding electrolyte to form ion channels, connecting an external circuit to form electronic channels, and carrying out electrochemical reaction to obtain the silicon-based alloy particles;
in the step 3, the non-silicon component removing method comprises the steps of preparing the alloy particles obtained in the step 2 into electrodes, assembling the electrodes, electrolyte and a counter electrode into a primary battery, charging, and removing the non-silicon component in the alloy to obtain nano silicon-based material particles;
or in the step 3, the non-silicon component is removed by adding an active reaction substance to react with the alloy particles obtained in the step 2, and removing ions embedded into the silicon-based particles in the step 1 to obtain the nano silicon-based material particles.
2. The method for preparing a nano silicon-based material according to claim 1, wherein: in the step 1, the particle size D0 of the silicon-based particles is more than or equal to 1 μm, and the silicon-based particles comprise at least one of simple substance silicon, silicon oxide and silicon-based composite material.
3. The method for preparing a nano silicon-based material according to claim 1, wherein: in step 1, the new element comprises at least one of lithium, sodium, aluminum and magnesium.
4. The method for preparing a nano silicon-based material according to claim 1, wherein: potential difference exists between the power source substance and the silicon-based particles, and when an electronic channel and an ion channel are formed at the same time, ions in the power source substance are separated and automatically embedded into the silicon-based particles; or the power source substance is capable of providing ions capable of reacting with the silicon-based particles to form silicon-based alloy particles; the electrolyte can conduct ions extracted from the power source material.
5. The method for preparing a nano silicon-based material according to claim 1, wherein: the power source substance includes at least one of a positive electrode material capable of supplying ions, a metal substance as an electrode material; the electrolyte comprises a solute and a solvent, the solute comprises ions removed from the power source substance, and the concentration of the solute is 0.1-1.5 mol/L.
6. The method for preparing a nano silicon-based material according to claim 5, wherein: the metal substance used as the electrode material comprises at least one of metal lithium, metal sodium, metal potassium, metal magnesium, metal aluminum and metal zinc, and the electrolyte is at least one of lithium ion battery electrolyte, lithium sulfur battery electrolyte, sodium ion battery electrolyte, aluminum ion battery electrolyte, zinc ion battery electrolyte and magnesium ion battery electrolyte.
7. The method for preparing a nano silicon-based material according to claim 1, wherein: in the step 2, the external force applying mode comprises at least one of ball milling, high-speed shearing, high-pressure impact and high-speed impact.
8. The method for preparing a nano silicon-based material according to claim 1, wherein: furthermore, the electrode prepared from the alloy particles contains a conductive agent, the electrolyte can conduct ions extracted from the alloy particles, the counter electrode can receive the ions extracted from the alloy particles, and the electrode made from the alloy particles is electrically insulated from the counter electrode.
9. The method for preparing a nano silicon-based material according to claim 1, wherein: the active reaction substance comprises at least one of water, acid, alkali and organic solvent.
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