CN108878823B - Preparation method of metal olivine coated nano silicon - Google Patents

Preparation method of metal olivine coated nano silicon Download PDF

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CN108878823B
CN108878823B CN201810653668.4A CN201810653668A CN108878823B CN 108878823 B CN108878823 B CN 108878823B CN 201810653668 A CN201810653668 A CN 201810653668A CN 108878823 B CN108878823 B CN 108878823B
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张宇
杨庆
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Foshan Griffin New Energy Co.,Ltd.
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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 preparation method of metal olivine coated nano silicon. The method comprises the following steps: 1) mixing metal oxide powder with SiO under the condition that the oxygen content is less than 1000ppmxUniformly mixing the powder to obtain a mixture; 2) isolating oxygen, and calcining the mixture to obtain a compound; 3) isolating oxygen, and performing ball milling on the compound to obtain the metal olivine coated nano silicon. The preparation method is simple and easy to operate and control, simultaneously uses few organic solvents in the synthesis process, is beneficial to protecting the environment, has low cost of coating raw materials, is beneficial to saving the cost, is suitable for industrial large-scale production, and has outstanding electrochemical performance in silicon cathode materials.

Description

Preparation method of metal olivine coated nano silicon
Technical Field
The invention relates to the field of nano materials, in particular to a preparation method of metal olivine coated nano silicon.
Background
Lithium ion batteries using lithium cobaltate, lithium iron phosphate, nickel cobalt manganese and the like as positive electrode materials have the advantages of high working voltage, large specific energy, no pollution, light weight, small volume, no memory effect, rapid charge and discharge, long service life and the like, are widely used for portable electronic products such as mobile phones and the like, and are also applied to electric vehicles and hybrid electric vehicles on a large scale to become one of the most valuable energy storage devices in the 21 st century.
At present, the carbon negative electrode material has the advantages of good conductivity, low lithium intercalation potential, excellent cycle performance, rich resources, low price, no toxicity, no pollution and the like, and is an ideal lithium ion battery negative electrode material. However, the widely used carbon negative electrode material has a problem of low specific capacity (theoretical capacity 372 mAh/g). The development requirements of high-capacity and high-power secondary batteries cannot be met, and the improvement of the performance of lithium batteries is restricted, so that the development of novel battery cathode materials becomes one of the current important research directions.
Silicon has large lithium storage capacity (4200mAh/g) and is rich in earth content and is an ideal negative electrode material of a lithium ion battery, but the silicon material generates huge volume change (300%) in the lithium ion lithium intercalation and deintercalation process, so that the negative electrode structure is broken and pulverized in the circulation process to cause the loss of lithium deintercalation capacity, and the negative electrode material is exfoliated from a current collector to cause the deterioration of current collection characteristics. Meanwhile, the volume expansion also causes the SEI film formed on the surface to be very unstable, resulting in lower coulombic efficiency. Thereby restricting the application of silicon as a negative electrode material.
At present, there are many methods for improving the cycling stability of silicon materials, such as: the nano silicon is used as a cathode material, and when the size of silicon particles is smaller than 150nm, the volume expansion effect begins to be reduced, so that the nano silicon as an active substance can show better electrochemical performance in initial circulation, but the nano silicon can generate an agglomeration phenomenon along with the circulation, and thus the capacity is attenuated very quickly in the subsequent circulation process. And the direct preparation of nano silicon as a negative electrode material is expensive, and the possibility of large-scale commercialization is not high, CN106784762A provides a preparation method and application of a nano silicon array negative electrode material, and although the nano silicon array relieves the volume expansion to a certain extent and improves the cycle stability, the method has various steps and is difficult to apply in large scale.
In addition, coating modification of silicon materials is common, CN106784763A discloses a method for preparing a porous oxide-coated battery silicon cathode, the number of active species on the surface of a silicon-based material is controlled by passivating the surface of the silicon-based material, and then the surface of the silicon-based material is coated with nano porous oxides of different thicknesses by using a vapor atomic layer deposition technique, CN106159215A discloses a silicon cathode material and a preparation method thereof, and a cathode comprising the silicon cathode material and a lithium ion battery use a liquid phase method to perform two-layer carbon coating on 1-100 μm silicon powder, CN107845800A uses a sputtering deposition technique to perform nano tin nitride coating on a silicon substrate carrying a silicon array, the coated silicon material improves the electrochemical performance of the battery to a certain extent, but the related coating method is very complex, and graphene or nitride is used as a coating layer, the cost is high, the condition requirement is harsh, and the related gas phase atomic layer deposition technology and sputtering deposition technology are only limited to laboratory preparation at present, so that the method is not beneficial to industrial mass production.
How to modify a silicon-based material by using a simple and efficient synthesis method so as to effectively improve the electrochemical performance of a lithium ion battery taking the silicon-based material as a cathode has important practical significance for further developing the silicon-based cathode material and realizing large-scale industrial production.
Disclosure of Invention
The invention aims to provide a preparation method of metal olivine coated nano silicon. The preparation method is simple, easy to operate and control, low in raw material cost, beneficial to saving cost and suitable for industrial large-scale production.
The technical scheme adopted by the invention is as follows:
a preparation method of metal olivine coated nano silicon comprises the following steps:
1) mixing metal oxide powder with SiO under the condition that the oxygen content is less than 1000ppmxUniformly mixing the powder to obtain a mixture;
2) isolating oxygen, and calcining the mixture to obtain a compound;
3) isolating oxygen, and performing ball milling on the compound to obtain the metal olivine coated nano silicon;
wherein x is more than or equal to 0.2 and less than or equal to 1.5. Preferably, 0.8. ltoreq. x.ltoreq.1.2.
Preferably, the metal oxide powder in step 1) is mixed with SiOxThe mass ratio of the powder is (0.1-10): 1.
preferably, the metal oxide powder in step 1) is mixed with SiOxThe mass ratio of the powder is (0.5-4): 1.
more preferably, the metal oxide powder in step 1) is mixed with SiOxThe mass ratio of the powder is (0.5-2.5): 1.
wherein, too much metal oxide can reduce the capacity performance of the material, and less metal oxide can not obviously improve the first coulombic efficiency of the product.
Preferably, the particle diameter D50 of the metal oxide powder in the step 1) is 0.02-20 μm.
Preferably, the particle diameter D50 of the metal oxide powder in the step 1) is 0.1-10 μm.
More preferably, the particle diameter D50 of the metal oxide powder in the step 1) is 1-5 μm.
Preferably, SiO in step 1)xThe particle diameter D50 of the powder is 0.1-20 μm.
Preferably, SiO in step 1)xThe particle diameter D50 of the powder is 0.5-10 μm.
More preferably, SiO in step 1)xThe particle diameter D50 of the powder is 1-8 μm.
Undersize metal oxides and SiOxThe particle size of the powder increases the cost and increases the SiOxThe material is exposed in the air and oxidized, and the excessive particle size increases the energy consumption of the subsequent sand grinding process, which is not beneficial to the full contact and mixing of the materials.
Preferably, the metal oxide in step 1) is selected from at least one of magnesium oxide, calcium oxide, lithium oxide, iron oxide and aluminum oxide.
Preferably, the particle size D50 of the mixture in step 1) is less than or equal to 150 nm.
The sufficiently small particle size of the mixture facilitates thorough mixing between the different raw materials.
Preferably, the calcination in step 2) is carried out until a crystalline-structured metal olivine coating is formed.
Wherein, in order to achieve the calcining effect of the step 2), the calcining conditions can be as follows: the calcination temperature is 700-1400 ℃, the calcination time is 0.2-10 h, and more preferably, the calcination conditions can be as follows: the calcining temperature is 900-1400 ℃, and the calcining time is 0.5-6 h.
Preferably, the ball milling rotation speed in the step 3) is 400-450 r/min, and the ball milling time is 8-16 h.
Preferably, the particle size D50 of the metal olivine coated nano silicon obtained in the step 3) is 50-200 nm.
More preferably, the particle size D50 of the metal olivine coated nano silicon obtained in the step 3) is 80-180 nm.
Sufficiently small particles improve the stability of the material during battery cycling.
Wherein the nano-silicon is a crystal structure nano-silicon, and D50 represents: particles having a particle size greater than 50% of its particle size and less than 50% of its particle size are expressed as average particle sizes; d90 represents 90% of the particles having a particle size smaller than it.
The invention has the beneficial effects that:
1. the coating layer which takes the metal olivine as the main component is coated on the surface of the nano silicon, so that the problem of volume expansion of the nano silicon is effectively relieved, and when the nano silicon is used as a silicon negative electrode material, the circulation stability of the nano silicon in the charge and discharge process is improved, and the stable and efficient exertion of the electrochemical performance is ensured.
2. The preparation method is simple, easy to operate and control, simultaneously uses few organic solvents in the synthesis process, is beneficial to protecting the environment, has low cost of coating raw materials, is beneficial to saving the cost, and is suitable for industrial large-scale production.
Drawings
FIG. 1 is a Scanning Electron Micrograph (SEM) of a material prepared according to example 1 of the present invention;
FIG. 2 is a graph of the first charge and discharge of a comparative example material of the present invention;
FIG. 3 is a graph of the first charge and discharge curves of the material prepared in example 1 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples. It will also be understood that the following examples are included merely for purposes of further illustrating the invention and are not to be construed as limiting the scope of the invention, as the invention extends to insubstantial modifications and adaptations of the invention following in the light of the principles set forth herein. The specific process parameters and the like of the following examples are also only one example of suitable ranges, and the skilled person can make a selection within the suitable ranges through the description herein, and are not limited to the specific data of the following examples.
Example 1
A preparation method of metal olivine coated nano silicon comprises the following steps:
1) under the protection of nitrogen or argon, mixing light magnesium oxide powder with the particle size D50 of 2 mu m and the purity of 99% and silicon oxide (SiO) powder with the particle size D50 of 5 mu m according to the mass ratio of 3: 2, weighing, uniformly mixing, putting into a ball milling tank, adding absolute ethyl alcohol to enable the solid content of the solution to reach 30%, ball milling for 20 hours in a high-energy ball mill at the ball milling rotation speed of 450r/min, heating in a vacuum drying oven at 100-150 ℃, and removing the absolute ethyl alcohol to obtain a mixture with D50 of 150 nm;
2) placing the mixture in a tubular furnace, heating to 1150 ℃ at the speed of 5 ℃/min, and calcining for 2h in nitrogen atmosphere to obtain a forsterite-coated compound;
3) mixing the compound obtained in the step 2) with absolute ethyl alcohol to obtain a solution with the solid content of 30%, and performing high-energy ball milling for 12 hours in a nitrogen atmosphere, wherein the ball milling rotating speed is set to be 450r/min, so as to obtain the nano silicon coated with the attapulgite with the particle size D50 of 150 nm.
Examples 2 to 7
The procedure is as in example 1, the starting materials and reaction conditions are set up in Table 1 below, and those not mentioned in Table 1 correspond to those of example 1:
TABLE 1
Figure GDA0002532410110000041
Figure GDA0002532410110000051
Comparative example
A preparation method of nano silicon material comprises the following steps:
1) weighing 5kg of amorphous silicon with the particle size D50 of 5 microns, adding 17kg of absolute ethyl alcohol, ball-milling for 20 hours in a high-energy ball mill at the ball-milling rotation speed of 450r/min, heating in a vacuum drying oven at 100-150 ℃, and removing the absolute ethyl alcohol to obtain amorphous silicon with the particle size D50 of 150 nm;
2) placing the amorphous silicon obtained in the step 1) in a tubular furnace, heating to 1150 ℃ at the speed of 5 ℃/min, and calcining for 2h in nitrogen atmosphere;
3) mixing the substance obtained in the step 2) with absolute ethyl alcohol to obtain a solution with the solid content of 30%, and performing high-energy ball milling for 12 hours in a nitrogen atmosphere, wherein the ball milling rotating speed is set to be 450r/min, so as to obtain the nano silicon material with the particle size D50 of 150 nm.
1. And (3) morphology characterization:
FIG. 1 is a scanning electron micrograph of the material prepared in example 1 of the present invention. As can be seen from FIG. 1, the material prepared by the method has a laminated structure formed by stacking sheet crystal units with regular structures, wherein the sheet units have different particle sizes, and the particle size is about 50-200 nm.
2. And (3) testing electrical properties:
respectively taking the positive electrode material and the metal lithium as the negative electrode in the embodiment 1 and the comparative example to manufacture the performance of the half-cell test material, taking PVDF as a binder and activated carbon as a conductive agent, wherein the mass percentages of the positive electrode material, the metal lithium, the PVDF as a binder, the activated carbon as a conductive agent are 50: 30: 20, taking NMP as a solvent, stirring to prepare slurry, uniformly coating the slurry on an aluminum foil by using a coating machine, drying to prepare a positive plate, wherein the electrolyte is 1M LiPF6Dissolving in EC/DMC (1: 1, V/V), using metal lithium as a negative electrode, respectively assembling into CR2016 batteries in a glove box filled with argon, and performing constant current charge-discharge test on the batteries at a current density of 150mA/g within a voltage range of 0.01-3V, wherein the test results are shown in figure 2 and figure 3.
As can be seen from fig. 2 and 3: the electrochemical performance of the embodiment and the comparative example is greatly different, the first specific discharge capacity of the comparative example is only about 700mAh/g, the first specific discharge capacity of the embodiment is about 1700mAh/g which is 2.43 times that of the comparative example, the specific capacity of the comparative example when the comparative example is charged to 2V is only 260mAh/g, the specific capacity of the embodiment is about 1290mAh/g which is about 5 times that of the comparative example, and the fact shows that the metal olivine coated nano silicon material prepared by the method has more excellent electrochemical performance compared with the common nano silicon material.

Claims (4)

1. A preparation method of metal olivine coated nano silicon is characterized by comprising the following steps: the method comprises the following steps:
1) mixing metal oxide powder with SiO under the condition that the oxygen content is less than 1000ppmxUniformly mixing the powder, and performing ball milling to obtain a mixture;
2) isolating oxygen, and calcining the mixture to obtain a compound;
3) isolating oxygen, and performing ball milling on the compound to obtain the metal olivine coated nano silicon;
wherein x is more than or equal to 0.2 and less than or equal to 1.5;
the metal oxide in the step 1) is at least one selected from magnesium oxide, calcium oxide, lithium oxide and aluminum oxide, the particle size D50 of the mixture is less than or equal to 150nm, and the metal oxide powder and SiO in the step 1) are mixedxThe mass ratio of the powder is (0.5-2.5): 1;
step 2) calcining the metal olivine to form a metal olivine coating layer with a crystal structure, wherein the calcining temperature is 900-1400 ℃, and the calcining time is 0.5-6 h;
the particle size D50 of the metal olivine coated nano silicon obtained in the step 3) is 50-200 nm.
2. The method of claim 1, wherein: the particle size D50 of the metal oxide powder in the step 1) is 0.02-20 μm.
3. The method of claim 1, wherein: SiO in step 1)xThe particle diameter D50 of the powder is 0.1-20 μm.
4. The production method according to claim 3, characterized in that: SiO in step 1)xThe particle diameter D50 of the powder is 0.5-10 μm.
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