CN110649234A - Preparation method of silicon-based negative electrode material with high coulombic efficiency - Google Patents

Preparation method of silicon-based negative electrode material with high coulombic efficiency Download PDF

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CN110649234A
CN110649234A CN201910775331.5A CN201910775331A CN110649234A CN 110649234 A CN110649234 A CN 110649234A CN 201910775331 A CN201910775331 A CN 201910775331A CN 110649234 A CN110649234 A CN 110649234A
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silicon
preparation
coulombic efficiency
steps
following
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林少雄
周勇岐
王辉
许家齐
高玉仙
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Hefei Gotion High Tech Power Energy Co Ltd
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Hefei Guoxuan High Tech Power Energy Co Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • H01M4/366Composites as layered products
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/38Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386Silicon or alloys based on silicon
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • H01M4/625Carbon or graphite
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention relates to a preparation method of a silicon-based negative electrode material with high coulombic efficiency.A reducing substance is uniformly permeated into the prepared silicon-based material, and no obvious crystalline phase separation state can be generated in the material, so that the stress caused by volume change of the material in the lithium desorption and insertion process is reduced, the material pulverization phenomenon can be effectively reduced, and the material cycle performance is improved; after the main silicon-based structure is reduced by a reducing substance, a silicon crystal phase has higher lithium insertion capacity and first efficiency in the first charge-discharge process, and a silicate crystal phase reduces the consumption of lithium ions in the use process of the material and improves the first coulombic efficiency of the material; the surface coated carbon layer can effectively reduce the surface defects of the granulating material, and improve the conductivity and uniformity of the material, thereby improving the cycle performance of the silicon-based material.

Description

Preparation method of silicon-based negative electrode material with high coulombic efficiency
Technical Field
The invention relates to the field of silicon-based anode materials, in particular to a preparation method of a silicon-based anode material with high coulombic efficiency.
Background
The lithium ion battery is a battery system with the best comprehensive performance at present, has the characteristics of high specific energy, long cycle life, small volume, light weight, no memory effect, no pollution and the like, and is widely applied to information technology, aerospace, portable electronic products and electric automobiles; with the progress and development of various fields, the energy density of the existing lithium ion battery cannot meet the market demand, people start to improve the energy density from multiple aspects, and research and development of a high-specific-capacity negative electrode material is one of effective ways.
In the existing lithium ion battery cathode materials, the graphite materials are mainly commercially applied at present, the theoretical specific capacity is about 372mAh/g, and the requirements of high-tech products on the lithium ion batteries can not be met gradually; silicon has ultrahigh theoretical specific capacity of about 3579mAh/g, which is about 10 times of the theoretical capacity of the conventional graphite cathode, and the material has wide sources in nature, so the silicon is known to be one of the cathode materials most likely to replace graphite.
However, the silicon material has a significant disadvantage that the application of silicon in the lithium ion battery is limited to a certain extent because the phenomena of pulverization and shedding gradually occur in the cycle process of the lithium ion battery along with about 300% volume change in the processes of lithium insertion and lithium removal; the theoretical capacity of the silicon protoxide material is lower than that of the silicon material, and is only about 2300mAh/g, but the silicon protoxide material can also meet the requirement of the current lithium ion battery, and the volume effect is relatively small (about 200%) in the processes of lithium intercalation and lithium deintercalation, so that the silicon protoxide material is easier to realize a major breakthrough in the technical field and complete the commercialization promotion.
Disclosure of Invention
The invention aims to provide a preparation method of a silicon-based negative electrode material with high coulombic efficiency.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a silicon-based anode material with high coulombic efficiency comprises the following steps:
s1, coating a film on the surface of the silicon oxide material by taking the reducing substance as a target material;
s2, calcining the silicon monoxide material obtained in the step S1 in an inert atmosphere to obtain solid powder;
s3, carrying out acid washing and water washing treatment on the solid powder to remove impurities on the surface of the solid powder;
and S4, carbonizing and coating the solid powder obtained in the S3 to obtain the silicon-based negative electrode material with high coulomb efficiency.
Further, the silicon monoxide is SiO0.5-1.2Particle diameter D50=0.5-10 μm, specific surface area 1.0-3.5m2/g。
Further, the reducing substance is one or more of lithium powder, sodium powder, magnesium powder, lithium oxide, lithium carbonate, lithium hydroxide, sodium oxide, sodium carbonate, sodium hydroxide, magnesium oxide, magnesium carbonate and magnesium hydroxide.
Further, the specific method for coating the surface of the silicon monoxide material in S1 includes magnetron sputtering coating, plasma coating, reactive ion plating or multi-arc ion plating.
Further, the thickness of the plating film of the reducing substance in S1 is 30-300 nm.
Further, the inert atmosphere is nitrogen, argon or helium.
Furthermore, the calcining condition of S2 is 500-1300 ℃, and the temperature rising speed is 3-20 ℃/min.
Further, the acid adopted in the acid washing in S3 is one or more of hydrochloric acid, sulfuric acid, nitric acid, oxalic acid, acetic acid, boric acid, and phosphoric acid.
Further, the carbonization coating method in S4 is a gas phase or solid phase coating method.
Further, the carbonized-coated carbon source in S4 is one or more of asphalt, phenolic resin, epoxy resin, methane, ethane, acetylene, natural gas, toluene, acetonitrile, and ethanol.
The invention has the beneficial effects that:
according to the invention, a target material bombardment mode is utilized, a layer of reducing substance film is prepared on the surface of a silicon oxide substrate, then calcination is carried out, the surface reducing substance can uniformly permeate into the silicon oxide substrate in the sintering process to form a silicon and silicate crystalline phase, the silicon crystalline phase ensures the lithium intercalation and deintercalation capacity of the material, the silicate crystalline phase can inhibit the volume expansion in the lithium intercalation and deintercalation process of the silicon crystalline phase, and the silicate crystalline phase is preformed before the lithium intercalation and deintercalation of the material, so that the lithium ion consumption of a lithium ion battery in the lithium intercalation and deintercalation process is reduced; finally, a carbon coating layer is added on the surface.
Reducing substances are uniformly permeated into the silicon-based material prepared by the method, no obvious crystalline phase separation state can occur in the material, the stress caused by volume change of the material in the lithium desorption and insertion process is reduced, the material pulverization phenomenon can be effectively reduced, and the material cycle performance is improved; after the main silicon-based structure is reduced by a reducing substance, a silicon crystal phase has higher lithium insertion capacity and first efficiency in the first charge-discharge process, and a silicate crystal phase reduces the consumption of lithium ions in the use process of the material and improves the first coulombic efficiency of the material; the surface coated carbon layer can effectively reduce the surface defects of the granulating material, and improve the conductivity and uniformity of the material, thereby improving the cycle performance of the silicon-based material.
Drawings
Fig. 1 is an SEM image of a high coulombic efficiency silicon-based negative electrode material prepared in example 1;
FIG. 2 is an XRD pattern of a silicon-based anode material with high coulombic efficiency prepared in example 1;
fig. 3 is a charge-discharge curve of the silicon-based negative electrode material with high coulombic efficiency prepared in example 1.
Detailed Description
The invention will be further illustrated with reference to specific embodiments:
example 1:
taking metal lithium as a target material of a magnetron sputtering coating machine, fixing silica powder with 50g D50=1 μm in a sample chamber, and adjusting the vacuum degree in the equipment to be 5.0 x 10-6Torr, the general sputtering pressure is 30 millitorr, the sample heating temperature is 650 ℃, and a metal lithium coating with the thickness of 80nm is sputtered under the condition that the substrate rotates at 5 rpm/min; placing the sputtered coating material in a high-temperature sintering furnace, continuously introducing argon as protective gas, sintering at 600 ℃ for 10h to obtain reduced silicon protoxide material, adding excessive dilute hydrochloric acid for cleaningThirdly, washing the materials with excessive deionized water for five times, performing suction filtration, placing in a vacuum oven at 90 ℃ for 5 hours, and performing vacuum drying; and (3) taking 30g of a dried sample, adding 5g of asphalt, uniformly grinding, and then putting into a tube furnace to sinter for 3 hours at 1000 ℃ under the argon atmosphere to finally obtain the finished product of the silicon-based negative electrode material SiO @ M/C.
Preparing a negative pole piece by mixing the silicon-based negative pole material SiO @ M/C slurry in the embodiment 1, wherein the ratio of SiO @ M/C: SP: PAA =8:1:1, high-speed stirring speed of 2000rpm, stirring time of 30min, coating by using a small-sized laboratory coater, drying the pole piece in an oven at 90 ℃ overnight, and drying the pole piece according to the proportion of 1.5g/cm3And (3) compacting and rolling the cut pieces, preparing SiO and SiO/C material pole pieces by the same preparation process, and assembling 2016 type button cells. And discharging to 50mV with a constant current of 100 muA, and then charging to 1.5V with a constant current of 100 muA to carry out a button cell test. And respectively carrying out SEM appearance and XRD diffraction peak tests on the SiO @ M/C material.
And (3) electrochemical performance testing: FIG. 3 is a graph showing the first charging curve of the three button cells, wherein the lithium intercalation capacity of the SiO material is 2208.6mAh/g, the lithium deintercalation capacity is 779.3mAh/g, and the first efficiency is 35.28%; the lithium insertion capacity of the SiO/C material is 2095.4mAh/g, the lithium removal capacity is 1391.7mAh/g, and the first efficiency is 66.42%; the SiO @ M/C material has the lithium insertion capacity of 1532.2mAh/g, the lithium removal capacity of 1168.9mAh/g and the first efficiency of 76.29%. Through the test of three groups of materials, the SiO material has the defects of obviously incapability of removing lithium and low first efficiency although having higher lithium storage capacity; the conventional modified SiO/C material has obvious capacity performance improvement and first efficiency improvement, but is still low; finally, the silicon-based material prepared by the material subjected to metal reduction and spray granulation and carbon coating is slightly deficient in capacity exertion of the material, but the first efficiency obviously improved can provide higher capacity exertion and energy density for the preparation of the full cell.
FIG. 1 is a SEM appearance representation diagram of a SiO @ M/C material, and shows that the material forms nearly spherical particles after spray granulation, the surface is a compact structure after carbon coating, no obvious material defects exist, and the coating effect is good. FIG. 2 is an XRD diffraction pattern of a SiO @ M/C material, and as can be seen by comparing diffraction patterns of pure Si, the SiO material has an obvious crystal Si diffraction peak after reduction and high temperature, other miscellaneous peaks are mainly silicate diffraction peaks, and the expansion of the silicon-based material is buffered through a three-layer structure of silicate, graphite and carbon coating in the material, so that the material is a negative electrode material with high coulomb efficiency.
Example 2:
taking magnesium carbonate as a target material of a magnetron sputtering coating machine, fixing 80g D50=3 μm of silicon oxide powder in a sample chamber, and adjusting the vacuum degree in the equipment to be 4.0 x 10-6Torr, the general sputtering pressure is 20 millitorr, the sample heating temperature is 700 ℃, and a magnesium carbonate coating with the thickness of 30nm is sputtered under the condition that the substrate rotates at 5 rpm/min; placing the sputtered coating material in a high-temperature sintering furnace, continuously introducing argon as protective gas, sintering at the high temperature of 800 ℃ for 6 hours to obtain reduced silicon protoxide material, adding excessive dilute sulfuric acid to clean for three times, then cleaning the material with excessive deionized water for five times, performing suction filtration, placing in a vacuum oven at the temperature of 90 ℃ for 5 hours, and performing vacuum drying; and (3) taking 30g of a dried sample, adding 10g of phenolic resin, grinding uniformly, placing the sample into a tube furnace, sintering for 3h at 900 ℃ under the argon atmosphere, and finally obtaining the finished product of the silicon-based negative electrode material SiO @ M/C. (Material characterization test and electrochemical Performance test results were substantially the same as in example 1.)
Example 3:
taking lithium carbonate powder as a target material of a plasma coating machine, fixing silica powder with the diameter of 50g D50=5 μm in a sample chamber, and adjusting the vacuum degree in equipment to be 5.0 x 10-7Torr, the general sputtering pressure is 50 millitorr, the sample heating temperature is 600 ℃, and a lithium carbonate coating with the thickness of 150nm is sputtered under the condition that the substrate rotates at 10 rpm/min; placing the sputtered coating material in a high-temperature sintering furnace, continuously introducing helium gas as protective gas, sintering at 700 ℃ for 8h to obtain reduced silicon protoxide material, adding excessive acetic acid to clean for three times, then cleaning the material with excessive deionized water for five times, performing suction filtration, placing in a vacuum oven at 90 ℃ for 5h, and performing vacuum drying; and (3) putting 30g of the dried sample into a tube furnace, introducing helium gas as protective gas, heating to 850 ℃, simultaneously introducing 0.8L/min of helium gas and 0.8L/min of methane gas, sintering for 3h, and naturally cooling to obtain the finished product of the silicon-based negative electrode material SiO @ M/C. (Material characterization)Test, electrochemical Performance test substantially the same as in example 1)
The above-mentioned embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solution of the present invention by those skilled in the art should fall within the protection scope defined by the claims of the present invention without departing from the spirit of the present invention.

Claims (10)

1. A preparation method of a silicon-based negative electrode material with high coulombic efficiency is characterized by comprising the following steps: the method comprises the following steps:
s1, coating a film on the surface of the silicon oxide material by taking the reducing substance as a target material;
s2, calcining the silicon monoxide material obtained in the step S1 in an inert atmosphere to obtain solid powder;
s3, carrying out acid washing and water washing treatment on the solid powder to remove impurities on the surface of the solid powder;
and S4, carbonizing and coating the solid powder obtained in the S3 to obtain the silicon-based negative electrode material with high coulomb efficiency.
2. The preparation method of the silicon-based anode material with high coulombic efficiency according to claim 1, wherein the preparation method comprises the following steps: the silicon monoxide is SiO0.5-1.2Particle diameter D50=0.5-10 μm, specific surface area 1.0-3.5m2/g。
3. The preparation method of the silicon-based anode material with high coulombic efficiency according to claim 1, wherein the preparation method comprises the following steps: the reducing substance is one or more of lithium powder, sodium powder, magnesium powder, lithium oxide, lithium carbonate, lithium hydroxide, sodium oxide, sodium carbonate, sodium hydroxide, magnesium oxide, magnesium carbonate and magnesium hydroxide.
4. The preparation method of the silicon-based anode material with high coulombic efficiency according to claim 1, wherein the preparation method comprises the following steps: the specific method for coating the surface of the silicon monoxide material in the step S1 comprises magnetron sputtering coating, plasma coating, reactive ion plating or multi-arc ion plating.
5. The preparation method of the silicon-based anode material with high coulombic efficiency according to claim 1, wherein the preparation method comprises the following steps: the thickness of the plating film of the reducing substance in the S1 is 30-300 nm.
6. The preparation method of the silicon-based anode material with high coulombic efficiency according to claim 1, wherein the preparation method comprises the following steps: the inert atmosphere is nitrogen, argon or helium.
7. The preparation method of the silicon-based anode material with high coulombic efficiency according to claim 1, wherein the preparation method comprises the following steps: the calcination condition of S2 is 500-1300 ℃, and the temperature rise speed is 3-20 ℃/min.
8. The preparation method of the silicon-based anode material with high coulombic efficiency according to claim 1, wherein the preparation method comprises the following steps: the acid adopted in the acid washing in the S3 is one or more of hydrochloric acid, sulfuric acid, nitric acid, oxalic acid, acetic acid, boric acid and phosphoric acid.
9. The preparation method of the silicon-based anode material with high coulombic efficiency according to claim 1, wherein the preparation method comprises the following steps: the carbonization coating method in S4 is a gas phase or solid phase coating method.
10. The preparation method of the silicon-based anode material with high coulombic efficiency according to claim 9, wherein the method comprises the following steps: the carbonized and coated carbon source in the S4 is one or more of asphalt, phenolic resin, epoxy resin, methane, ethane, acetylene, natural gas, toluene, acetonitrile and ethanol.
CN201910775331.5A 2019-08-21 2019-08-21 Preparation method of silicon-based negative electrode material with high coulombic efficiency Pending CN110649234A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113363432A (en) * 2021-04-21 2021-09-07 万向一二三股份公司 Negative plate containing silicon-based negative electrode material with high initial coulombic efficiency and lithium ion battery
CN113410448A (en) * 2021-06-25 2021-09-17 广东凯金新能源科技股份有限公司 Silicon monoxide composite negative electrode material of lithium ion battery and preparation method thereof
CN114744166A (en) * 2022-02-25 2022-07-12 深圳市翔丰华科技股份有限公司 Preparation method of pre-lithiated silica composite material

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WO2012105669A1 (en) * 2011-01-31 2012-08-09 Dow Corning Toray Co., Ltd. Method for manufacturing a carbon surface-coated silicon-containing carbon-based composite material
CN102779988A (en) * 2012-08-06 2012-11-14 常州大学 Composite negative electrode material coating modification method of lithium ion battery
CN105189352A (en) * 2013-09-02 2015-12-23 株式会社Lg化学 Porous silicon based particles, method for preparing same and anode active material comprising same
CN108269979A (en) * 2017-12-28 2018-07-10 合肥国轩高科动力能源有限公司 A kind of sub- silicon/silicon/lithium metasilicate composite negative pole material of oxidation and preparation method thereof
CN108493438A (en) * 2018-04-27 2018-09-04 天津巴莫科技股份有限公司 A kind of lithium ion battery SiOxBase composite negative pole material and preparation method thereof

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Publication number Priority date Publication date Assignee Title
WO2012105669A1 (en) * 2011-01-31 2012-08-09 Dow Corning Toray Co., Ltd. Method for manufacturing a carbon surface-coated silicon-containing carbon-based composite material
CN102779988A (en) * 2012-08-06 2012-11-14 常州大学 Composite negative electrode material coating modification method of lithium ion battery
CN105189352A (en) * 2013-09-02 2015-12-23 株式会社Lg化学 Porous silicon based particles, method for preparing same and anode active material comprising same
CN108269979A (en) * 2017-12-28 2018-07-10 合肥国轩高科动力能源有限公司 A kind of sub- silicon/silicon/lithium metasilicate composite negative pole material of oxidation and preparation method thereof
CN108493438A (en) * 2018-04-27 2018-09-04 天津巴莫科技股份有限公司 A kind of lithium ion battery SiOxBase composite negative pole material and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113363432A (en) * 2021-04-21 2021-09-07 万向一二三股份公司 Negative plate containing silicon-based negative electrode material with high initial coulombic efficiency and lithium ion battery
CN113410448A (en) * 2021-06-25 2021-09-17 广东凯金新能源科技股份有限公司 Silicon monoxide composite negative electrode material of lithium ion battery and preparation method thereof
CN114744166A (en) * 2022-02-25 2022-07-12 深圳市翔丰华科技股份有限公司 Preparation method of pre-lithiated silica composite material

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