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 PDFInfo
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 42
- 239000010703 silicon Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 57
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 11
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 34
- 238000000576 coating method Methods 0.000 claims description 28
- 239000011248 coating agent Substances 0.000 claims description 24
- 239000000843 powder Substances 0.000 claims description 15
- 239000010405 anode material Substances 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000012071 phase Substances 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000013077 target material Substances 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 239000001307 helium Substances 0.000 claims description 5
- 229910052734 helium Inorganic materials 0.000 claims description 5
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 5
- 102220043159 rs587780996 Human genes 0.000 claims description 5
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 238000007733 ion plating Methods 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 4
- 239000001095 magnesium carbonate Substances 0.000 claims description 4
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 4
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 3
- 239000010426 asphalt Substances 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 238000003763 carbonization Methods 0.000 claims description 2
- 238000010000 carbonizing Methods 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 2
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 2
- 229940031958 magnesium carbonate hydroxide Drugs 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 239000003345 natural gas Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000007747 plating Methods 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 2
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 2
- 239000007790 solid phase Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 11
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 11
- 239000002210 silicon-based material Substances 0.000 abstract description 8
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 abstract description 7
- 238000003780 insertion Methods 0.000 abstract description 7
- 230000037431 insertion Effects 0.000 abstract description 7
- 239000013078 crystal Substances 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 4
- 230000008859 change Effects 0.000 abstract description 3
- 238000010298 pulverizing process Methods 0.000 abstract description 3
- 238000003795 desorption Methods 0.000 abstract description 2
- 238000005191 phase separation Methods 0.000 abstract description 2
- 238000005245 sintering Methods 0.000 description 9
- 238000009831 deintercalation Methods 0.000 description 6
- 238000009830 intercalation Methods 0.000 description 6
- 230000002687 intercalation Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
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- 239000000377 silicon dioxide Substances 0.000 description 2
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- 238000002441 X-ray diffraction Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- H01M4/386—Silicon or alloys based on silicon
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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
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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
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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
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.
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