CN111342027A - Hydroxyl modified amorphous SiOx shell layer coated nano-silicon negative electrode material, preparation method and preparation method of negative electrode piece - Google Patents
Hydroxyl modified amorphous SiOx shell layer coated nano-silicon negative electrode material, preparation method and preparation method of negative electrode piece Download PDFInfo
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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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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- 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
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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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
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Abstract
The invention discloses a hydroxyl modified amorphous SiOx shell layer coated nano silicon lithium ion battery cathode material, which is nano simple substance silicon particles coated with a layer of 0.5-5 nm hydroxyl modified amorphous SiOx layer, wherein the particle size of the nano simple substance silicon particles is 20-60 nm. The material is prepared by the following method: 1) preparing an ethanol aqueous solution; 2) adding nano silicon particles into the solution, and performing ultrasonic treatment to form uniform suspension; 3) standing the suspension, performing ultrasonic treatment 4), separating the nano silicon particles from the ethanol water solution, and drying the nano silicon material in a vacuum oven to obtain the material. The material prepared by the invention is coated by amorphous SiOx with uniform thickness, has good inhibition effect on silicon volume expansion and low reversible capacity, and the preparation method used by the invention has the advantages of simple process, stable product performance, high yield, controllable cost, recyclable material and environmental friendliness.
Description
Technical Field
The invention belongs to the field of battery preparation, and particularly relates to a hydroxyl modified amorphous SiOx shell layer coated nano-silicon negative electrode material, a preparation method and a preparation method of a negative electrode sheet.
Background
With the development of society, people have higher and higher requirements on energy, and in the past decades, widely used non-renewable fossil energy is facing a plurality of problems such as exhaustion, environmental pollution and the like. The utilization of renewable green energy sources such as wind energy, solar energy and nuclear energy is considered to be an effective solution to the increasingly serious environmental problems and energy supply and demand contradictions. However, most renewable energy sources face the problems of uneven regional distribution, poor stability and the like, and generally need to be converted into electric energy to be effectively utilized. Therefore, the development of rechargeable batteries with high energy density, high power density, fast cycling rate, long service life and low cost has great significance for the development of the human society. The negative electrode material is one of important factors determining the capacity of the battery, the theoretical capacity of the positive electrode material of the lithium ion battery at present has a small promotion space, and the improvement of the reversible specific capacity of the negative electrode material is an effective way for improving the overall capacity of the battery. Currently available lithium ion negative electrode materials include carbon materials, silicon-based materials, transition metal oxides, and the like. The silicon element is abundant in earth crust, low in cost, mature in preparation process, environment-friendly in use process and low in oxidation-reduction potential. The theoretical capacity of Si reaches 3579mAh/g (Li15Si) at room temperature. However, the silicon negative electrode has large volume expansion (about 300%) after lithium intercalation, which causes particle shedding, pole piece pulverization and SEI film cracking, and is expressed in low cycle efficiency and low capacity retention rate in battery performance.
Recent research proves that after the silicon material is subjected to nanocrystallization, the deformation stress caused by volume expansion can be reduced, so that the problem of pulverization and shedding of a silicon negative electrode is relieved, the cycling stability of the electrode is improved, and high discharge capacity is maintained. So far, forms such as zero-dimensional nanospheres, one-dimensional nanorods, two-dimensional nanofilms and the like have been reported. However, the size of the silicon material is not enough to meet the requirement of the lithium ion battery negative electrode on the cycling stability.
Hu et al 4 showed that the silicon nanowire modified by the nano-silicon particles as the negative electrode material of the lithium ion battery has the advantage of high capacity. The one-dimensional nano structure can still keep the original structure after charge and discharge cycles, and the discharge capacity keeps 2000mA h g < -1 > after 30 cycles of cycles. However, the porous nanowire structure is complex to prepare, high in cost, difficult to realize mass production and application, high in cyclicity, and incapable of meeting economic benefit and environmental protection requirements.
Disclosure of Invention
The nano silicon negative electrode material prepared by the invention has the advantages that the hydroxyl group with uniform thickness is used for modifying the amorphous SiOx coating layer, the inhibition effect on silicon volume expansion is good, the reversible capacity is low, the preparation method is simple in process, the cost is controllable, the material can be recycled, and the environment is more friendly.
The invention also provides a preparation method of the hydroxyl modified amorphous SiOx shell-coated nano-silicon negative electrode material.
More necessary, the invention also provides a negative plate prepared by the hydroxyl modified amorphous SiOx shell layer coated nano-silicon negative electrode material
A hydroxyl modified amorphous SiOx shell layer coated nano silicon lithium ion battery negative electrode material comprises:
the hydroxyl modified amorphous SiOx shell layer coated nano silicon lithium ion battery cathode material is nano simple substance silicon particles coated with a layer of 0.5-5 nm hydroxyl modified amorphous SiOx layer.
Preferably, the hydroxyl modified amorphous SiOx shell layer coated nano silicon lithium ion battery cathode material is nano simple substance silicon particles coated with a 1-3 nm hydroxyl modified amorphous SiOx layer.
Preferably, the particle size of the nano elemental silicon particles is 20-60 nm.
A preparation method of a hydroxyl modified amorphous SiOx shell layer coated nano silicon lithium ion battery negative electrode material comprises the following steps:
1) preparing an ethanol aqueous solution;
2) adding nano silicon particles into the solution, and performing ultrasonic treatment to uniformly distribute the nano silicon particles in the solution to form uniform suspension;
3) standing the suspension, and carrying out ultrasonic treatment on the suspension every 10 hours to avoid silicon particle deposition;
4) and separating the nano silicon particles from the ethanol water solution, and drying the nano silicon material in a vacuum oven to obtain the hydroxyl modified amorphous SiOx shell-coated nano silicon negative electrode material.
The thickness of the coating layer of the prepared hydroxyl modified amorphous SiOx shell layer coated nano silicon negative electrode material is 0.5-5 nm, and 1-3 nm is preferred.
Wherein, the preferable preparation method comprises the following steps:
1) preparing ethanol into 2-10 vol% ethanol water solution, preferably 10 vol%;
2) adding nano silicon particles into the solution, wherein the mass of the nano silicon is calculated according to that 10ml of ethanol water solution corresponds to 1g of nano silicon, and performing ultrasonic treatment to uniformly disperse the nano silicon particles in the solution;
3) standing the suspension, and carrying out ultrasonic treatment on the suspension every 10 hours to avoid silicon particle deposition;
4) and separating the nano silicon particles from the ethanol water solution, and drying the nano silicon material in a vacuum oven to obtain the hydroxyl modified amorphous SiOx shell-coated nano silicon negative electrode material.
Preferably, the nano silicon particles have a particle size of 20 to 60 nm.
Preferably, the time of the ultrasound in step 2) is 15-60 minutes, preferably 30 minutes, the power is 70-100kWh, and the frequency is 40 Hz.
Preferably, the conditions of step 3) are: standing, and performing ultrasonic dispersion treatment once every 10 hours; the time of each ultrasound is 15-30 minutes, the power is 70-100kWh, and the frequency is 40 Hz.
Preferably, after the steps 4) and 4-8 days, separating the nano silicon particles from the ethanol solution by centrifugation or suction filtration, and drying the nano silicon particles in a vacuum oven at 180 ℃ for 12 hours to obtain the hydroxyl modified amorphous SiOx shell-coated nano silicon negative electrode material.
Preferably, the preparation method of the hydroxyl-modified amorphous SiOx shell layer-coated nano-silicon lithium ion battery negative electrode material comprises the following steps:
1) preparing 50ml of ethanol aqueous solution with the concentration of 5 vol%;
2) adding 5g of nano silicon particles into the solution, and performing ultrasonic treatment to uniformly disperse the nano silicon particles in the solution, wherein the ultrasonic treatment time is 30 minutes, the frequency is 40Hz, and the power is 100 kWh;
3) standing, performing ultrasonic dispersion treatment once every 10 hours, wherein the ultrasonic time is 30 minutes, the frequency is 40Hz, and the power is 100 kWh;
4) and after 4-8 days, separating the nano silicon particles from the ethanol solution by centrifugation or suction filtration, and drying the nano silicon particles in a vacuum oven at 180 ℃ for 12 hours to obtain the hydroxyl modified amorphous SiOx shell-coated nano silicon negative electrode material.
A preparation method of a negative plate comprises the following steps:
firstly, dispersing the hydroxyl modified amorphous SiOx shell-coated nano-silicon negative electrode material prepared by the preparation method of any one of embodiments 1 to 7, a conductive agent (Surper P) and a binder (CMC) in a 5 vol% ethanol aqueous solution at a mass ratio of 8:1:1, wherein the volume ratio of the ethanol aqueous solution to the nano-silicon is 2 ml: 0.08g (calculated by the proportion of 2ml of solution per 0.08g of nano-silicon in time when the dosage of the ethanol aqueous solution is calculated), stirring for 6 hours, stirring by using a magnetic stirrer or other stirrers, fully and uniformly mixing to prepare slurry, and then uniformly coating the slurry on a copper foil by using a coating machine, wherein the thickness of the copper foil is 15 microns;
after coating, transferring the pole piece to a vacuum drying oven, vacuumizing, drying for 10 hours at 90 ℃, punching a circular pole piece with the diameter of 12mm from the dried pole piece by using a manual sheet punching machine, weighing the mass of the pole piece, and removing the mass of copper foil, conductive agent and adhesive to obtain the single pole piece loaded with the hydroxyl modified amorphous SiOx shell coated nano silicon negative electrode material.
Compared with the background art, the preparation method of the negative electrode material provided by the invention is simple in process, low in cost, environment-friendly, capable of being prepared in a large scale and excellent in performance.
According to the invention, the SiOx film containing hydroxyl modification can be formed on the surface of the nano silicon by the process, and the thickness of the coating film is controllable from 0.1 nm to 5 nm;
the SiOx film is generated by hydration/dehydration reaction of silicon, the content of Si4+ and hydroxyl in the coating film can be increased by prolonging the treatment time, the increase of Si4+ means that more lithium silicate and lithium oxide can be generated irreversibly in the coating layer during lithiation, the lithium ion conductivity of the lithium oxide is higher than 9, the improvement of the reversible capacity of the material is facilitated, and the hydroxyl can form firmer bonding with a bonding agent, so that the structural stability of the electrode is enhanced. Therefore, the scheme is possible;
according to the invention, a small amount of ethanol is added to improve the wettability of the nano silicon in the aqueous solution, so that the nano silicon is further well dispersed into the aqueous solution through dispersion technologies such as ultrasonic, and the aqueous solution is made to fully wet the nano silicon particles, so that water and the surfaces of the nano silicon particles are fully reacted.
The purpose of regulating and controlling the electrochemical performance of the silicon cathode is achieved by controlling the reaction time, and the optimal thickness of the SiOx film modified by hydroxyl contained on the surface of the prepared nano silicon particles is 1-2 nanometers, so that the SiOx film can be well applied to the lithium ion battery cathode.
Drawings
FIG. 1 is a HRTEM image of a hydroxyl-modified amorphous SiOx shell-coated nano-silicon negative electrode material;
FIG. 2 is an XPS spectrum of a hydroxyl-modified amorphous SiOx shell-coated nano-silicon negative electrode material;
FIG. 3 is an XRD spectrum of a hydroxyl-modified amorphous SiOx shell-coated nano-silicon negative electrode material;
FIG. 4 is an FTIR spectrum of a hydroxyl-modified amorphous SiOx shell-coated nano-silicon negative electrode material;
FIG. 5 is a comparison graph of the cycle performance of the hydroxyl-modified amorphous SiOx shell-coated nano-silicon negative electrode material;
FIG. 6 is an SEM image of a pole piece made of a recycled hydroxyl-modified amorphous SiOx shell-coated nano-silicon negative electrode material.
Detailed Description
The core of the invention is to provide a preparation method of the pH-sensitive fluorescent carbon dots capable of being controllably adjusted. In order that those skilled in the art will better understand the disclosure, the invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
Description of raw material sources:
nano-silicon particles a: nanometer simple substance silicon with particle diameter of 20-60nm and brand name of Aladdin-S130843
Nano-silicon particles B: the nano simple substance silicon has the particle size range of 100-200nm and the brand number of Aladdin-S130844
Surper P: conductive carbon black with brand number of Annaiji-W010903
CMC: binder, sodium carboxymethylcellulose (Novus-NBP 1-86786 PEP)
The rest materials are commercially available.
Example 1
The preparation method of the hydroxyl modified amorphous SiOx shell-coated nano silicon negative electrode material comprises the following steps:
1) adding deionized water into 2ml of absolute ethyl alcohol to 50ml of absolute ethyl alcohol, and uniformly stirring to obtain 4 vol% of ethyl alcohol solution;
2) adding 5g of nano silicon particles A with the particle size of 20nm to 60nm into the ethanol solution, and carrying out ultrasonic treatment for 30 minutes by using an ultrasonic cleaner to uniformly disperse the nano silicon particles A in the solution, wherein the ultrasonic power is 100kWh, and the frequency is 40 Hz;
3) standing, and performing ultrasonic treatment once again every 10 hours, wherein the ultrasonic treatment time is 30 minutes, the ultrasonic power is 100kWh, and the frequency is 40 Hz;
4) and after 96 hours (4 days), separating the nano silicon particles A from the solution by using a suction filtration device, and drying the nano silicon particles A in a vacuum oven at 180 ℃ for 12 hours to obtain the hydroxyl modified amorphous SiOx shell layer coated nano silicon negative electrode material.
Example 2
The preparation method of the hydroxyl modified amorphous SiOx shell-coated nano silicon negative electrode material comprises the following steps:
1) adding deionized water into 2ml of absolute ethyl alcohol to 50ml of absolute ethyl alcohol, and uniformly stirring to obtain 4 vol% of ethyl alcohol solution;
2) adding 0.8g of nano silicon particles A with the particle size of 20nm to 60nm into the ethanol solution, and carrying out ultrasonic treatment for 30 minutes by using an ultrasonic cleaner so as to uniformly disperse the nano silicon particles A in the solution, wherein the ultrasonic power is 100kWh, and the frequency is 40 Hz;
3) standing, and performing ultrasonic treatment once again every 10 hours, wherein the ultrasonic treatment time is 30 minutes, the ultrasonic power is 100kWh, and the frequency is 40 Hz;
4) and 192 hours (8 days), separating the nano silicon particles A from the solution by using a suction filtration device, and drying the nano silicon particles A in a vacuum oven at 180 ℃ for 12 hours to obtain the hydroxyl modified amorphous SiOx shell layer coated nano silicon negative electrode material.
Example 3
1) Adding deionized water into 5ml of absolute ethyl alcohol to 50ml of absolute ethyl alcohol, and uniformly stirring to obtain 10 vol% of ethyl alcohol solution;
2) adding 0.8g of nano silicon particles A with the particle size of 20nm to 60nm into the ethanol solution, and carrying out ultrasonic treatment for 30 minutes by using an ultrasonic cleaner so as to uniformly disperse the nano silicon particles A in the solution, wherein the ultrasonic power is 100kWh, and the frequency is 40 Hz;
3) standing, and performing ultrasonic treatment once again every 10 hours, wherein the ultrasonic treatment time is 30 minutes, the ultrasonic power is 100kWh, and the frequency is 40 Hz;
4) and after 96 hours (4 days), separating the nano silicon particles A from the solution by using a suction filtration device, and drying the nano silicon particles A in a vacuum oven at 180 ℃ for 12 hours to obtain the hydroxyl modified amorphous SiOx shell layer coated nano silicon negative electrode material.
Example 4
1) 1ml of absolute ethyl alcohol is taken, deionized water is added to 50ml, and the mixture is stirred uniformly to prepare 2 vol% of ethyl alcohol solution;
2) adding 0.8g of nano silicon particles A with the particle size of 20nm to 60nm into the ethanol solution, and carrying out ultrasonic treatment for 30 minutes by using an ultrasonic cleaner so as to uniformly disperse the nano silicon particles A in the solution, wherein the ultrasonic power is 100kWh, and the frequency is 40 Hz;
3) standing, and performing ultrasonic treatment once again every 10 hours, wherein the ultrasonic treatment time is 30 minutes, the ultrasonic power is 100kWh, and the frequency is 40 Hz;
4) and after 96 hours (4 days), separating the nano silicon particles A from the solution by using a suction filtration device, and drying the nano silicon particles A in a vacuum oven at 180 ℃ for 12 hours to obtain the hydroxyl modified amorphous SiOx shell layer coated nano silicon negative electrode material.
Comparative example 1
The preparation method of the hydroxyl-free modified amorphous SiOx shell-coated nano silicon negative electrode material comprises the following steps:
1) taking 5g of nano silicon particles A in 50ml of 5 vol% hydrofluoric acid aqueous solution, and carrying out ultrasonic treatment for 15min, wherein the ultrasonic power is 100kWh, and the frequency is 40 Hz;
2) filtering the treated nano silicon particles by suction, and washing for 3-5 times by using deionized water;
3) and after cleaning, separating the nano silicon particles A from the solution by using suction filtration, and drying the nano silicon particles in a vacuum oven at 180 ℃ for 12 hours to obtain the hydroxyl-free modified amorphous SiOx shell-coated nano silicon negative electrode material.
Comparative example 2
The preparation method of the hydroxyl modified amorphous SiOx shell-coated nano silicon negative electrode material comprises the following steps:
1) adding deionized water into 2ml of absolute ethyl alcohol to 50ml of absolute ethyl alcohol, and uniformly stirring to obtain 4 vol% of ethyl alcohol solution;
2) adding 5g of nano silicon particles A with the particle size of 20nm to 60nm into the ethanol solution, and carrying out ultrasonic treatment for 30 minutes by using an ultrasonic cleaner to uniformly disperse the nano silicon particles A in the solution, wherein the ultrasonic power is 100kWh, and the frequency is 40 Hz;
3) and separating the nano silicon particles A from the solution by using a suction filtration device, and drying the nano silicon particles A in a vacuum oven at 180 ℃ for 12 hours to obtain the hydroxyl modified amorphous SiOx shell layer coated nano silicon negative electrode material.
Comparative example 3
The preparation method of the hydroxyl modified amorphous SiOx shell-coated nano silicon negative electrode material comprises the following steps:
1) adding deionized water into 2ml of absolute ethyl alcohol to 50ml of absolute ethyl alcohol, and uniformly stirring to obtain 4 vol% of ethyl alcohol solution;
2) adding 5g of nano silicon particles A with the particle size of 20nm to 60nm into the ethanol solution, and carrying out ultrasonic treatment for 30 minutes by using an ultrasonic cleaner to uniformly disperse the nano silicon particles A in the solution, wherein the ultrasonic power is 100kWh, and the frequency is 40 Hz;
3) standing, and performing ultrasonic treatment once again every 10 hours, wherein the ultrasonic treatment time is 30 minutes, the ultrasonic power is 100kWh, and the frequency is 40 Hz;
4) and 768 hours (32 days), separating the nano silicon particles A from the solution by using a suction filtration device, and drying the nano silicon particles A in a vacuum oven at 180 ℃ for 12 hours to obtain the hydroxyl modified amorphous SiOx shell layer coated nano silicon negative electrode material.
Comparative example 4
1) Adding deionized water into 2ml of absolute ethyl alcohol to 50ml of absolute ethyl alcohol, and uniformly stirring to obtain 4 vol% of ethyl alcohol solution;
2) adding 5g of nano silicon particles A with the particle size of 20nm to 60nm into the ethanol solution, and carrying out ultrasonic treatment for 30 minutes by using an ultrasonic cleaner to uniformly disperse the nano silicon particles A in the solution, wherein the ultrasonic power is 100kWh, and the frequency is 40 Hz;
3) standing, and performing ultrasonic treatment once again every 10 hours, wherein the ultrasonic treatment time is 30 minutes, the ultrasonic power is 100kWh, and the frequency is 40 Hz;
4) and 384 hours (16 days), separating the nano silicon particles A from the solution by using a suction filtration device, and drying the nano silicon particles A in a vacuum oven at 180 ℃ for 12 hours to obtain the hydroxyl modified amorphous SiOx shell layer coated nano silicon negative electrode material.
Comparative example 5
The preparation method of the hydroxyl modified amorphous SiOx shell-coated nano silicon negative electrode material comprises the following steps:
1) adding deionized water into 2ml of absolute ethyl alcohol to 50ml of absolute ethyl alcohol, and uniformly stirring to obtain 4 vol% of ethyl alcohol solution;
2) adding 5g of nano silicon particles B with the particle size ranging from 20nm to 60nm into the ethanol solution, and carrying out ultrasonic treatment for 30 minutes by using an ultrasonic cleaner to uniformly disperse the nano silicon particles B in the solution, wherein the ultrasonic power is 100kWh, and the frequency is 40 Hz;
4) and after 96 hours (4 days), separating the nano silicon particles B from the solution by using a suction filtration device, and drying the nano silicon particles A in a vacuum oven at 180 ℃ for 12 hours to obtain the hydroxyl modified amorphous SiOx shell layer coated nano silicon negative electrode material. Experimental example 1
Microstructural characterisation
The nano silicon anode materials prepared in the example 1, the example 2, the comparative example 2 and the comparative example 3 are scanned under a high-power transmission electron microscope (HR-TEM, model number JEOL JEM-2100) to obtain an HRTEM image, which is shown in FIG. 1.
The upper left picture of fig. 1 is the sem scan of comparative example 2, the upper right picture of fig. 1 is the sem scan of example 1, the lower left picture of fig. 1 is the sem scan of example 2, and the lower right picture of fig. 1 is the sem scan of comparative example 3.
As can be seen from fig. 1, the amorphous SiOx coating of the nano-silicon anode materials prepared in examples 1 to 2 is more uniform and the thickness thereof is significantly thicker than that of the nano-silicon anode materials prepared in comparative examples 2 to 3, the nano-silicon coating thickness of comparative example 2 is 0.7nm, the nano-silicon coating thickness of example 1 is 1.5nm, the nano-silicon coating thickness of example 2 is 2nm, and the nano-silicon coating thickness of comparative example 3 is 2.8 nm.
The nano silicon cathode materials prepared in the examples 1-2 and the comparative examples 2-3 were analyzed by X-ray photoelectron spectroscopy (equipment model: ESCALB 250, using Al target K α as a radiation source) to obtain XPS spectra shown in FIG. 2 (wherein (a) corresponds to the comparative example 2, (b) corresponds to the example 1, (c) corresponds to the example 2, and (d) corresponds to the comparative example 2), and the X-ray diffraction technique (equipment model: Rigaku Minifflex 600, scanning range: 10-90 °, step length: 5 °/min, radiation source: copper target K α to obtain FIG. 3.
As can be seen from the results of fig. 2 and 3, the hydroxyl group modified amorphous SiOx shell coated nano silicon anode material prepared in example 1-2 has a significantly increased content of Si4+ in the coating layer and a more significant degree of atomic arrangement order than the nano silicon anode material prepared in comparative example 2-3.
Scanning the nano silicon negative electrode materials prepared in the embodiments 1, 2 and 3 by an infrared spectrometer (the model number of the equipment is BRUKER TENSOR37) to obtain FTIR spectra attached to fig. 4, wherein as can be seen from the FTIR spectra, the surfaces of the silicon negative electrode materials prepared in the embodiments 1 and 2 are modified by hydroxyl groups, and the number of the hydroxyl groups is gradually increased along with the extension of the processing time, so that the bonding effect of silicon particles and a binder is enhanced, the SEI film is stabilized, and the reaction activity of the silicon negative electrode material is improved;
experimental example 2
The hydroxyl modified amorphous SiOx shell-coated nano-silicon negative electrode materials prepared in examples 1-3 and comparative examples 1-5 were prepared into batteries by the following methods:
(1) preparing a negative plate: firstly, dispersing a hydroxyl modified amorphous SiOx shell layer coated nano silicon negative electrode material, a conductive agent (Surper P) and a binder (CMC) in a 5 vol% ethanol aqueous solution according to a mass ratio of 8:1:1, wherein the volume of the ethanol aqueous solution and the ratio of nano silicon are 2 ml: 0.08g (calculated according to the proportion of 2ml of solution to 0.08g of nano-silicon in time when the dosage of the ethanol aqueous solution is calculated), stirring for 6 hours by using a magnetic stirrer, fully and uniformly mixing to prepare slurry, and then uniformly coating the slurry on a copper foil by using a coating machine, wherein the thickness of the copper foil is about 15 microns. After coating, the pole piece is transferred to a vacuum drying oven, and after vacuumizing, the pole piece is dried for 10 hours at 90 ℃. And (3) punching a circular pole piece with the diameter of 12mm from the dried pole piece by using a manual punching machine, weighing the mass of the pole piece, and removing the mass of the copper foil, the conductive agent and the adhesive to obtain the single pole piece loaded with the hydroxyl modified amorphous SiOx shell layer coated with the nano silicon negative electrode material.
(2) Assembling the battery: the pole piece is used as a working electrode, the lithium piece is used as a counter electrode, and the oxygen value of argon is lower than 0.1ppm at the water valueAnd assembling a 2032 type button battery in the atmosphere glove box. The battery diaphragm is a circular diaphragm made of a single-layer polypropylene material and having a diameter of 16mm, the electrolyte is a mixed solution of diethyl carbonate (DEC) and Ethylene Carbonate (EC) with a volume ratio of 1:1 as a solvent, and LiPF6As the lithium salt solute, the concentration was 1mol L-1. After the battery is assembled, the battery is kept stand for 10 hours, the electrochemical performance measurement is started after the pole piece is fully soaked by the electrolyte, the cycle performance of the material under the current density of 1A/g is measured, and the results are listed in Table 1.
Description of the test methods:
constant current Charge-Discharge Tests (Galvanostatic Charge-Discharge Tests) refer to charging and discharging a battery by adopting constant current, recording parameters such as voltage, capacity, time and the like of the battery, and can be used for testing the cycle performance and rate capability of an electrode material and analyzing lithiation and delithiation behaviors of the material. All battery performance tests related to the patent are carried out on a blue CT2001A device, the charge-discharge cut-off voltage is 2V and 0.01V respectively, the current density of the first 5 circles is 0.1A/g, the subsequent circulating current density is 1A/g, the calculation base number of the capacity retention rate is the first circle of the density cycle of 1A/g, and the test results are listed in Table 1.
TABLE 1
The data in the table show that when the preparation method of the hydroxyl modified amorphous SiOx shell-coated nano silicon negative electrode material obtained by the treatment method provided by the invention is used, the cycle performance and reversible capacity of the silicon negative electrode can be obviously improved. When the treatment time of the nano silicon particles and water is 4-8 days, the thickness of a coating layer formed on the surface of the nano silicon particles is 0.5-5 nanometers, and Si in the coating layer4+The content is lower than 50 percent, which can effectively relieve the volume expansion of the nano silicon and does not cause excessive irreversible loss of lithium ions. In addition, the proper amount of SiOH is beneficial to forming firm bonding among the bonding agent, the conductive agent and the silicon powder, so that the structural stability of the electrode is improved, and the overall conductivity is also improved.
The discharge capacity at different turns of comparative example 2, example 1, example 2 and comparative example 3 is shown in fig. 5, and it can be directly seen from fig. 5 that the thicker the coating layer is, the better the inhibition effect on the volume expansion of silicon is, and when the coating layer is too thick, the polarization is increased, and the reversible capacity is reduced;
the single pole piece after 500 cycles of scanning was scanned by a galvano scanner (model SU-70) to obtain the attached FIG. 6 (wherein (a) corresponds to comparative example 2, (b) corresponds to example 1, (c) corresponds to example 2, (d) corresponds to comparative example 2),
it can be seen that the monolithic pole piece made of the nano-silicon negative electrode material obtained in example 1-2 can still maintain the complete structure after 50 cycles, no obvious crack is observed, while the original sample of comparative example 1-2 has larger cracks and pulverized particles on the surface. The above results demonstrate that the coating layer can effectively improve the electrode stability, thereby improving the cycle performance.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A hydroxyl modified amorphous SiOx shell layer coated nano silicon lithium ion battery negative electrode material comprises:
the lithium ion battery cathode material is characterized in that the hydroxyl modified amorphous SiOx shell layer coated with the nano silicon lithium ion battery cathode material is nano simple substance silicon particles coated with a layer of 0.5-5 nm hydroxyl modified amorphous SiOx layer.
2. The hydroxyl-modified amorphous SiOx shell-coated nano-silicon lithium-ion battery negative electrode material of claim 1, wherein:
the particle size of the nano simple substance silicon particles is 20-60 nm.
3. The preparation method of the negative electrode material of the lithium ion battery with the hydroxyl-modified amorphous SiOx shell coating as in claim 1 or 2, which is characterized in that:
1) preparing an ethanol aqueous solution;
2) adding nano silicon particles into the solution, and performing ultrasonic treatment to uniformly distribute the nano silicon particles in the solution to form uniform suspension;
3) standing, and carrying out ultrasonic treatment on the silicon particles every 10 hours to avoid silicon particle deposition;
4) and separating the nano silicon particles from the ethanol water solution, and drying the nano silicon material in a vacuum oven to obtain the hydroxyl modified amorphous SiOx shell-coated nano silicon negative electrode material.
4. The method for preparing the negative electrode material of the hydroxyl-modified amorphous SiOx shell-coated nano-silicon lithium-ion battery of claim 3, wherein the method comprises the following steps:
1) preparing ethanol into 2-10 vol% ethanol water solution;
2) adding nano silicon particles into the solution, wherein the mass of the nano silicon is calculated according to that 1g of nano silicon corresponds to 10ml of ethanol aqueous solution, and uniformly dispersing the nano silicon particles in the solution by ultrasonic;
3) standing, and carrying out ultrasonic treatment on the silicon particles every 10 hours to avoid silicon particle deposition;
4) and separating the nano silicon particles from the ethanol water solution, and drying the nano silicon material in a vacuum oven to obtain the hydroxyl modified amorphous SiOx shell-coated nano silicon negative electrode material.
5. The method for preparing the negative electrode material of the hydroxyl-modified amorphous SiOx shell-coated nano-silicon lithium-ion battery of claim 3, wherein the method comprises the following steps:
the particle size of the nano silicon particles is 20-60 nm.
6. The method for preparing the negative electrode material of the hydroxyl-modified amorphous SiOx shell-coated nano-silicon lithium-ion battery of claim 5, wherein the method comprises the following steps:
the ultrasonic treatment in the step 2) is carried out for 15-60 minutes at a power of 70-100kWh and at a frequency of 40 Hz.
7. The method for preparing the negative electrode material of the hydroxyl-modified amorphous SiOx shell-coated nano-silicon lithium-ion battery of claim 5, wherein the method comprises the following steps:
the conditions of the step 3) are as follows: performing ultrasonic dispersion treatment once every 10 hours; the time of each ultrasound is 15-30 minutes, the power is 70-100kWh, and the frequency is 40 Hz.
8. The method for preparing the negative electrode material of the hydroxyl-modified amorphous SiOx shell-coated nano-silicon lithium-ion battery of claim 5, wherein the method comprises the following steps:
and 4) after 4-8 days, separating the nano silicon particles from the ethanol solution through centrifugation or suction filtration, and drying the nano silicon particles in a vacuum oven at 180 ℃ for 12 hours to obtain the hydroxyl modified amorphous SiOx shell layer coated nano silicon negative electrode material.
9. The method for preparing the negative electrode material of the hydroxyl-modified amorphous SiOx shell-coated nano-silicon lithium-ion battery of claim 5, wherein the method comprises the following steps:
1) preparing 50ml of ethanol aqueous solution with the concentration of 5 vol%;
2) adding 5g of nano silicon particles into the solution, and performing ultrasonic treatment to uniformly disperse the nano silicon particles in the solution, wherein the ultrasonic treatment time is 30 minutes, the frequency is 40Hz, and the power is 100 kWh;
3) standing, performing ultrasonic dispersion treatment once every 10 hours, wherein the ultrasonic time is 30 minutes, the frequency is 40Hz, and the power is 100 kWh;
4) and after 4 days, separating the nano silicon particles from the ethanol solution by centrifugation or suction filtration, and drying the nano silicon particles in a vacuum oven at 180 ℃ for 12 hours to obtain the hydroxyl modified amorphous SiOx shell layer coated nano silicon negative electrode material.
10. A preparation method of a negative plate comprises the following steps:
firstly, dispersing the hydroxyl modified amorphous SiOx shell-coated nano-silicon negative electrode material prepared by the preparation method of any one of embodiments 3-9, the conductive agent (Surper P) and the binder (CMC) in a 5 vol% ethanol aqueous solution at a mass ratio of 8:1:1, wherein the volume ratio of the ethanol aqueous solution to the nano-silicon is 2 ml: 0.08g, stirring for 6 hours, fully and uniformly mixing to prepare slurry, and then uniformly coating the slurry on a copper foil by using a coating machine, wherein the thickness is 15 microns;
after coating, transferring the pole piece to a vacuum drying oven, vacuumizing, drying for 10 hours at 90 ℃, punching a circular pole piece with the diameter of 12mm from the dried pole piece by using a manual sheet punching machine, weighing the mass of the pole piece, and removing the mass of copper foil, conductive agent and adhesive to obtain the single pole piece loaded with the hydroxyl modified amorphous SiOx shell coated nano silicon negative electrode material.
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