CN110993906A - Silicon-based lithium ion battery cathode material and preparation method thereof - Google Patents

Silicon-based lithium ion battery cathode material and preparation method thereof Download PDF

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CN110993906A
CN110993906A CN201911145442.4A CN201911145442A CN110993906A CN 110993906 A CN110993906 A CN 110993906A CN 201911145442 A CN201911145442 A CN 201911145442A CN 110993906 A CN110993906 A CN 110993906A
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nickel
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杜宁
雷雨
杨德仁
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Zhejiang University ZJU
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    • H—ELECTRICITY
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    • 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
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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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
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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Abstract

The invention discloses a silicon-based lithium ion battery cathode material and a preparation method thereof, wherein the silicon-based lithium ion battery cathode material comprises a substrate and a nano rod-shaped nickel-silicon core-shell array deposited on the substrate; the nano rod-shaped nickel-silicon core-shell array takes a nickel forward conical array as a core and takes silicon as a shell. The preparation method comprises the following steps: growing a nickel forward conical array on the surface of the pretreated substrate by an electrodeposition method; and depositing nano silicon outside the nickel forward conical array by adopting a vapor deposition method to obtain the silicon-based lithium ion battery cathode material. The silicon-based lithium ion battery cathode material disclosed by the invention is of a nano rod-shaped array structure which is uniform from top to bottom, has excellent initial specific capacity and cycling stability, and is expected to be widely applied in the field of lithium ion batteries.

Description

Silicon-based lithium ion battery cathode material and preparation method thereof
Technical Field
The invention relates to the technical field of lithium ion battery cathode materials, in particular to a silicon-based lithium ion battery cathode material and a preparation method thereof.
Background
In recent years, rapid development of portable electronic devices and electric vehicles has put higher demands on the performance of lithium ion batteriesHowever, conventional graphite anode materials are due to their lower theoretical capacity (374 mah.g)-1) The requirement in the field of electric vehicles has gradually been unsatisfied, and thus a new lithium ion battery cathode with high specific capacity, high safety, long service life and low cost has to be sought urgently.
Silicon (Si) has been considered as an anode material having great commercial utility because it has an extremely high theoretical reversible capacity (4200mAh g) as an anode material-1) And lower lithium ion intercalation voltage and lower production cost. However, silicon is easy to cause rapid change of electrode material volume in the charging and discharging process, and oxide materials are generally poor in conductivity, so that the silicon can not be popularized and applied on a large scale. In order to overcome the above defects of silicon, a refined structural design is required.
Chinese patent document No. CN 104201338A discloses a method for preparing a negative electrode of a lithium ion battery, which includes: (1) cobalt salt and urea are used as raw materials, and a cobaltous oxide nanowire array is synthesized on a substrate through a hydrothermal reaction combined with heat treatment; (2) and depositing an electrode material on the cobaltous oxide nanowire array to obtain the cathode of the lithium ion battery.
According to the technical scheme, the structure of the lithium ion battery cathode material is designed, the cobaltous oxide nanowire array is synthesized on the substrate through the combination of hydrothermal reaction and heat treatment, and then the cobaltous oxide nano-silicon core-shell structure composite nanomaterial is obtained through sputtering one layer of silicon. The structure of the cobaltous oxide-silicon core-shell structure composite nano material can well relieve the volume expansion of silicon in the lithium ion embedding and embedding process, and the cobaltous oxide nanowire array growing on the metal substrate can improve the conductivity of silicon and is also good for improving the multiplying power performance of a battery. However, after the prepared nanowire array is sputtered with silicon, the problem of 'heavy head and light foot' of the nanowire array can be caused due to sputtering operation, and a large amount of silicon is gathered at the head of the nanowire, so that the cobaltous oxide nano-silicon core-shell structure composite nanomaterial still has the problem of non-uniformity, and the cycle performance is degraded.
Disclosure of Invention
Aiming at the problems in the prior art, the invention discloses a silicon-based lithium ion battery cathode material and a preparation method thereof.
The specific technical scheme is as follows:
a silicon-based lithium ion battery cathode material comprises a substrate and a nano rod-shaped nickel-silicon core-shell array deposited on the substrate;
the nano rod-shaped nickel-silicon core-shell array takes a nickel forward conical array as a core and takes silicon as a shell.
The silicon-based lithium ion battery cathode material disclosed by the invention is of a nano rod-shaped nickel-silicon core-shell array structure, takes nickel as a core and silicon as a shell, has uniform upper and lower diameters, and avoids the problem of light weight of a nano rod array caused by a vapor deposition technology, so that the silicon-based lithium ion battery cathode material has excellent initial specific capacity and cycling stability.
Preferably:
the diameter of the bottom of the nickel regular conical array is 200-500 nm, and the ratio of the diameter of the bottom to the height is 1: 1-2;
the diameter of the nanorod nickel-silicon core-shell array is uniform from top to bottom, the diameter is 200-500 nm, and the ratio of the diameter of the bottom to the height is 1: 1 to 2.
Tests show that the silicon-based lithium ion battery negative electrode material with the size has better initial specific capacity and cycling stability.
The invention also discloses a preparation method of the silicon-based lithium ion battery cathode material, which comprises the following steps:
(1) growing a nickel forward conical array on the surface of the pretreated substrate by an electrodeposition method;
(2) and (2) depositing nano silicon outside the nickel forward conical array prepared in the step (1) by adopting a vapor deposition method to obtain the silicon-based lithium ion battery cathode material.
In the step (1):
the substrate is selected from a metal substrate or a nonmetal substrate deposited with metal;
the metal substrate can be a copper substrate, or a nonmetal substrate deposited with an ITO film can be selected.
The pretreatment comprises electrolytic oil removal, and specifically comprises the following steps:
and (3) placing the substrate in an alkaline degreasing agent, taking out the substrate, and then electrolyzing, pickling, washing and drying the substrate for later use.
The alkaline degreasing agent is used for removing oil stains on the surface of the metal substrate, and can be a commercially available product or a self-prepared product. Preferably, the alkaline degreasing agent consists of sodium carbonate, potassium hydroxide and a wetting agent.
Preferably, the electrolysis is, in particular: at 5Adm-2Is electrolyzed for 60s at the current density of (1).
The electrodeposition takes a substrate as an anode and a nickel plate as a cathode, and the adopted electrodeposition solution comprises nickel salt, a crystallization regulator and a buffering agent;
the pH value of the electrodeposition solution is 3-5, the pH value is adjusted by adding an alkaline substance, and ammonia water is preferably adopted for adjustment.
Preferably:
the nickel salt is selected from nickel chloride or nickel sulfate;
the crystallization regulator is selected from ammonium chloride and alkylamine with 1-12 carbon atoms, such as Ethylenediamine (EDA).
The buffer is selected from boric acid;
the molar ratio of the nickel salt to the crystallization regulator to the buffer is 1: 3-5: 0.2 to 1.0.
Preferably, the current density of the electrodeposition is 1-10 Adm-2The deposition time is 600-1200 s.
In the step (1), the composition and the deposition time of the electrodeposition solution are critical to the morphology of the nickel forward tapered array obtained by deposition, and tests show that the molar ratio of the nickel salt, the crystallization regulator and the buffer is 1: 3-5: 0.2-1.0, and controlling the deposition time to be 600-1200 s, so as to ensure that the diameter of the bottom of the prepared nickel regular cone array is 200-500 nm, and the ratio of the diameter of the bottom to the height is 1: 1-2; thereby providing the premise for finally preparing the high-performance silicon-based lithium ion battery cathode material.
It was also found by experiment that as the electrodeposition time increased, the diameter of the bottom of the resulting tapered array became larger and the height of the taper increased, and that when the deposition time exceeded 1200s, a portion of the tapered morphology broke.
Further preferably:
the electrodeposition solution comprises nickel chloride, ammonium chloride and boric acid according to a molar ratio of 1: 4: 0.5 of the mixture;
the electrodeposition time was 900 s.
Tests show that the finally prepared silicon-based lithium ion battery cathode material has better initial specific capacity and cycling stability by taking the nickel forward conical array prepared under the preferable technological conditions as a core.
In the step (2):
the vapor deposition method is selected from chemical vapor deposition or physical vapor deposition.
Preferably, the vapor phase deposition method is a magnetron sputtering method, the magnetron sputtering power is 40-200W, the working pressure is 0-20 Pa, and the sputtering time is 30-120 min.
Preferably, the magnetron sputtering power is 50-100W, and the working pressure is 1-10 Pa.
The magnetron sputtering time is too short, the deposition amount of silicon is too small, the conical shape is not completely coated, the active quality is low, and the battery capacity is low; the sputtering time is too long, the sputtered silicon excessively coats the substrate, and finally deposits into a block shape, so that the rod-shaped structure is lost, and the performance of the battery is reduced.
More preferably, the magnetron sputtering time is 60 min.
Still more preferably:
in the step (1):
the electrodeposition solution comprises nickel chloride, ammonium chloride and boric acid according to a molar ratio of 1: 4: 0.5 of the mixture;
the time of the electrodeposition is 900 s;
in the step (2):
the magnetron sputtering power is 80W, the working pressure is 2Pa, and the magnetron sputtering time is 60 min.
Tests show that under the re-optimized process parameters, the initial specific capacity and the cycling stability of the finally prepared silicon-based lithium ion battery negative electrode material are optimal.
Compared with the prior art, the invention has the following advantages:
the invention discloses a silicon-based lithium ion battery cathode material with a novel morphology, which is characterized in that a nickel forward conical array is taken as a core, silicon is taken as a shell, and a nanorod-shaped nickel-silicon core-shell array structure with uniform upper and lower diameters is formed, so that the problem that a silicon-based nanorod array with a core-shell structure prepared in the prior art is light in weight and has better initial specific capacity and cycling stability.
Drawings
FIG. 1 is an SEM picture of a nickel cone array prepared in example 1;
fig. 2 is an SEM picture of the negative electrode material of the silicon-based lithium ion battery prepared in example 1;
fig. 3 is electrical performance data for half cells assembled with the silicon-based lithium ion battery anode material prepared in example 5, and electrical performance data for half cells assembled with the silicon-based lithium ion battery anode material prepared in comparative example is given as a comparison.
Detailed Description
The present invention is further illustrated by the following specific examples, but the scope of the present invention is not limited to the following examples.
Example 1
Cutting the copper sheet into 4cm × 4cm squares, and removing the oil with an alkaline solution of 70g L-1Sodium carbonate 10g L-1Potassium hydroxide, 10g L-1And (3) ethanol. The copper substrate was coated on a 5Adm substrate-2Electrolyzing for 60s under the current density, taking out, pickling for 10-20s in 20% dilute sulfuric acid solution, washing with deionized water, and drying to obtain the cathode for electrodeposition. The anode is an electrolytic nickel plate with the purity of 99.9 percent, the thickness of the electrolytic nickel plate is 3mm, and the size of the electrolytic nickel plate is about 5cm multiplied by 5 cm. In the electrodeposition solution, 0.5mol L of boric acid-1The nickel chloride hexahydrate content is 1.0mol L-1Ammonium chloride 4.0mol L-1The pH was 4, and 10% ammonia water was used as a pH adjuster. Deposition Current 2Adm-2And the electrodeposition time is 600s, so that the nickel forward tapered array is obtained.
And carrying out magnetron sputtering on the obtained nickel conical array after vacuum drying. The magnetron sputtering power is 80W, the sputtering time is 30min, and the working pressure is 2 Pa. And obtaining the silicon-based negative electrode material which is marked as Ni @ Si core-shell array material.
The SEM image of the nickel forward tapered array prepared in this example is shown in fig. 1, and the diameter of the bottom of the nickel forward tapered array is 150nm, and the ratio of the diameter of the bottom to the height is 1: 1, uniformly depositing on the surface of the substrate.
The silicon-based negative electrode material prepared in the embodiment is of a nanorod array structure with uniform vertical dimensions, a nickel forward conical array is used as a core, silicon is used as a shell, the diameter of the bottom is 150nm, and the ratio of the diameter of the bottom to the height is 1: 1.
the silicon-based negative electrode material prepared in the embodiment is assembled into a half cell for cycle performance test. The battery coated with the silicon-based negative electrode material prepared in the example serves as a positive electrode, and a lithium sheet serves as a counter electrode. The loading amount of the active material on the pole piece is 0.03-0.08 mg/cm2。
The battery cycle test was conducted with a long cycle test at a current density of 400 mA/g. The battery performance test results are as follows: the first cycle discharge capacity is 2459mAh/g, the eleventh cycle discharge capacity is 869mAh/g, the first hundred cycle discharge capacity is 576mAh/g, and the capacity after one hundred cycles is only 66.3% (relative to the eleventh cycle).
Example 2
The preparation process was the same as in example 1, except that: adjusting the concentration of ammonium chloride in the electrodeposition solution to 3.0mol L-1。
Using the same test conditions as in example 1, the first cycle discharge capacity was tested to be 2312mAh/g, the eleventh cycle discharge capacity was 851mAh/g, the first hundred cycle discharge capacity was 366mAh/g, and the remaining capacity after one hundred cycles was 43.0% (relative to the eleventh cycle).
Example 3
The preparation process was the same as in example 1, except that: the concentration of ammonium chloride in the electrodeposition solutionAdjusted to 5.0mol L-1。
The same test conditions as in example 1 were used, and the first cycle discharge capacity was found to be 2458mAh/g, the eleventh cycle discharge capacity was found to be 892mAh/g, the first hundred cycle discharge capacity was found to be 402mAh/g, and the remaining capacity after one hundred cycles was found to be 45.1% (relative to the eleventh cycle).
Example 4
Cutting the copper sheet into 4cm × 4cm squares, and removing the oil with an alkaline solution of 70g L-1Sodium carbonate 10g L-1Potassium hydroxide, 10g L-1And (3) ethanol. The copper substrate was coated on a 5Adm substrate-2Electrolyzing for 60s at the current density of (1), taking out, pickling in 20% dilute sulfuric acid solution for 10-20s, washing with deionized water, and drying to obtain cathode for electrodeposition. The anode is an electrolytic nickel plate with the purity of 99.9 percent, the thickness of the electrolytic nickel plate is 3mm, and the size of the electrolytic nickel plate is about 5cm multiplied by 5 cm. In the electrodeposition solution, 0.5mol L of boric acid-1The nickel chloride hexahydrate content is 1.0mol L-1Ammonium chloride 4.0mol L-1And pH 4. 10% ammonia water and 10% hydrochloric acid as pH value regulator. Deposition Current 2Adm-2The electrodeposition time was 900 s.
And carrying out magnetron sputtering on the obtained nickel conical array after vacuum drying. The magnetron sputtering power is 80W, the sputtering time is 30min, and the working pressure is 2 Pa. Obtaining the Ni @ Si nuclear shell array material.
Through the test:
the diameter of the bottom of the nickel forward tapered array prepared in this example was 300nm, and the ratio of the diameter of the bottom to the height was 1: 2.
the silicon-based negative electrode material prepared in the embodiment is of a nanorod array structure with uniform vertical dimensions, a nickel forward conical array is used as a core, silicon is used as a shell, the diameter is 300nm, and the ratio of the diameter of the bottom to the height is 1: 2.
the silicon-based negative electrode material prepared in the embodiment is assembled into a half cell for cycle performance test. The battery coated with the silicon-based negative electrode material prepared in the example serves as a positive electrode, and a lithium sheet serves as a counter electrode. The loading capacity of the active material on the pole piece is 0.03-0.10 mg/cm2。
The battery cycle test was conducted with a long cycle test at a current density of 400 mA/g. The battery performance test results are as follows: the first cycle discharge capacity was 2389mAh/g, the eleventh cycle discharge capacity was 856mAh/g, the one hundred cycle discharge capacity was 732mAh/g, and the capacity remained only 85.5% after one hundred cycles (relative to the eleventh cycle).
Example 5
Cutting the copper sheet into 4cm × 4cm squares, and removing the oil with an alkaline solution of 70g L-1Sodium carbonate 10g L-1Potassium hydroxide, 10g L-1The wetting agent of (1). The copper substrate was coated on a 5Adm substrate-2Electrolyzing for 60s at the current density of (1), taking out, pickling in 20% dilute sulfuric acid solution for 10-20s, washing with deionized water, and drying to obtain cathode for electrodeposition. The anode is an electrolytic nickel plate with the purity of 99.9 percent, the thickness of the electrolytic nickel plate is 3mm, and the size of the electrolytic nickel plate is about 5cm multiplied by 5 cm. In the electrodeposition solution, 0.5mol L of boric acid-1The nickel chloride hexahydrate content is 1.0mol L-1Ammonium chloride 4.0mol L-1And pH 4. 10% ammonia water and 10% hydrochloric acid as pH value regulator. Deposition Current 2Adm-2The electrodeposition time was 900 s.
And carrying out magnetron sputtering on the obtained nickel conical array after vacuum drying. The magnetron sputtering power is 80W, the sputtering time is 60min, and the working pressure is 2 Pa. Obtaining the Ni @ Si nuclear shell array material.
Through the test:
the diameter of the bottom of the nickel forward tapered array prepared in this example was 300nm, and the ratio of the diameter of the bottom to the height was 1: 2.
an SEM image of the silicon-based negative electrode material prepared in this example is shown in fig. 2, where the silicon-based negative electrode material is a nanorod array structure with uniform vertical dimensions, a nickel forward conical array is used as a core, silicon is used as a shell, the diameter is about 300nm, and the ratio of the bottom diameter to the height is 1: 2.
the silicon-based lithium ion battery cathode material prepared in the embodiment is assembled into a half battery for cycle performance test. The battery coated with the silicon-based negative electrode material prepared in the example serves as a positive electrode, and a lithium sheet serves as a counter electrode. The loading capacity of the active material on the pole piece is 0.03-0.10 mg/cm2。
The battery cycle test was conducted with a long cycle test at a current density of 400 mA/g. The battery performance test results are as follows: the first cycle discharge capacity was 3345mAh/g, the eleventh cycle discharge capacity was 1167mAh/g, the first hundred cycle discharge capacity was 1112mAh/g, and the remaining capacity after one hundred cycles was 95.3% (relative to the eleventh cycle).
Because the magnetron sputtering time is short, the nickel array in the shape of a regular cone can be converted into the nano rod-shaped array with the same upper and lower sizes after the silicon shell is coated, but the change of the diameter and the length-diameter ratio of the bottom of the nano rod-shaped array can not be obviously caused, so that the sizes of the nano rod-shaped arrays obtained in the embodiments 4 and 5 after different magnetron sputtering times are close, but through an electrical property test, it can be found that the half cell assembled by the silicon-based lithium ion battery cathode material prepared with the magnetron sputtering time of 60min has higher initial discharge capacity and better cycle stability compared with the half cell assembled by the silicon-based lithium ion battery cathode material prepared with the.
Comparative example 1
Cutting the copper sheet into 4cm × 4cm squares, and removing the oil with an alkaline solution of 70g L-1Sodium carbonate 10g L-1Potassium hydroxide, 10g L-1The wetting agent of (1). The copper substrate was coated on a 5Adm substrate-2Electrolyzing for 60s at the current density of (1), taking out, pickling in 20% dilute sulfuric acid solution for 10-20s, washing with deionized water, drying, and performing magnetron sputtering. The magnetron sputtering power is 80W, the sputtering time is 60min, and the working pressure is 2 Pa. Obtaining the Si array material.
The Si array material prepared in the comparative example was assembled into a half cell for cycle performance testing. In which the Si array material-coated battery prepared in this comparative example was used as a positive electrode and a lithium plate was used as a counter electrode. The loading capacity of the active material on the pole piece is 0.03-0.10 mg/cm2。
The battery cycle test was conducted with a long cycle test at a current density of 400 mA/g. The battery performance test results are as follows: the first cycle discharge capacity is 1367mAh/g, the eleventh cycle discharge capacity is 371mAh/g, the first hundred cycle discharge capacity is 80mAh/g, and the capacity after one hundred cycles is only remained 21.6% (relative to the eleventh cycle).
Comparative example 2
The preparation process and process conditions were the same as in example 5 except that the concentration of ammonium chloride in the electrodeposition bath was adjusted to 2.0mol L-1。
Through the test:
the diameter of the bottom of the nickel forward tapered array prepared in this comparative example was 100nm, and the ratio of the diameter of the bottom to the height was 1: 5.
the silicon-based negative electrode material prepared by the comparative example is also of a nanorod array structure with uniform vertical dimensions, a nickel forward conical array is used as a core, silicon is used as a shell, the diameter is about 100nm, and the ratio of the bottom diameter to the height is 1: 5.
the same test conditions as in example 1 were used, and the first cycle discharge capacity was 2435mAh/g, the eleventh cycle discharge capacity was 670mAh/g, the first hundred cycle discharge capacity was 201mAh/g, and the remaining 30.0% of the capacity after one hundred cycles (relative to the eleventh cycle) was tested.

Claims (10)

1. The silicon-based lithium ion battery cathode material is characterized by comprising a substrate and a nano rod-shaped nickel-silicon core-shell array deposited on the substrate;
the nano rod-shaped nickel-silicon core-shell array takes a nickel forward conical array as a core and takes silicon as a shell.
2. The silicon-based lithium ion battery anode material of claim 1, wherein:
the diameter of the bottom of the nickel regular conical array is 200-500 nm, and the ratio of the diameter of the bottom to the height is 1: 1-2;
the diameter of the nanorod nickel-silicon core-shell array is uniform from top to bottom, the diameter is 200-500 nm, and the ratio of the diameter of the bottom to the height is 1: 1 to 2.
3. The preparation method of the silicon-based lithium ion battery anode material according to claim 1 or 2, characterized by comprising the following steps:
(1) growing a nickel forward conical array on the surface of the pretreated substrate by an electrodeposition method;
(2) and (2) depositing nano silicon outside the nickel forward conical array prepared in the step (1) by adopting a vapor deposition method to obtain the silicon-based lithium ion battery cathode material.
4. The method for preparing the silicon-based lithium ion battery anode material according to claim 3, wherein in the step (1), the pretreatment comprises electrolytic degreasing, specifically:
and (3) placing the substrate in an alkaline degreasing agent, taking out the substrate, and then electrolyzing, pickling, washing and drying the substrate for later use.
5. The method for preparing the silicon-based lithium ion battery negative electrode material according to claim 1, wherein in the step (1), the substrate is used as an anode and the nickel plate is used as a cathode in the electrodeposition, and the electrodeposition solution comprises nickel salt, a crystallization regulator and a buffer;
the pH value of the electrodeposition solution is 3-5.
6. The preparation method of the silicon-based lithium ion battery anode material according to claim 5, characterized in that:
the nickel salt is selected from nickel chloride or nickel sulfate;
the crystallization regulator is selected from ammonium chloride and alkylamine with 1-12 carbon atoms;
the buffer is selected from boric acid;
the molar ratio of the nickel salt to the crystallization regulator to the buffer is 1: 3-5: 0.2 to 1.0.
7. The preparation method of the silicon-based lithium ion battery anode material according to claim 1, wherein in the step (1), the current density of the electrodeposition is 1-10 Adm-2The deposition time is 600-1200 s.
8. The preparation method of the silicon-based lithium ion battery anode material according to claim 1, wherein in the step (2), the vapor deposition method is selected from chemical vapor deposition or physical vapor deposition.
9. The method for preparing the silicon-based lithium ion battery anode material according to claim 1, wherein the vapor deposition method is selected from a magnetron sputtering method;
the magnetron sputtering power is 40-200W, the working pressure is 0-20 Pa, and the sputtering time is 30-120 min.
10. The preparation method of the silicon-based lithium ion battery anode material according to any one of claims 1 to 9, characterized by comprising the following steps:
in the step (1):
the electrodeposition solution comprises nickel chloride, ammonium chloride and boric acid according to a molar ratio of 1: 4: 0.5 of the mixture;
the time of the electrodeposition is 900 s;
in the step (2):
the magnetron sputtering power is 50-100W, the working pressure is 1-10 Pa, and the time is 60 min.
CN201911145442.4A 2019-11-21 2019-11-21 Silicon-based lithium ion battery cathode material and preparation method thereof Pending CN110993906A (en)

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Application publication date: 20200410