CN117038928A - Silicon-based negative electrode material for lithium battery and preparation method thereof - Google Patents
Silicon-based negative electrode material for lithium battery and preparation method thereof Download PDFInfo
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- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 76
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000010703 silicon Substances 0.000 title claims abstract description 74
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000007773 negative electrode material Substances 0.000 title claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000010405 anode material Substances 0.000 claims abstract description 32
- 239000000203 mixture Substances 0.000 claims abstract description 32
- 239000011777 magnesium Substances 0.000 claims abstract description 30
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 19
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 14
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 14
- 239000000391 magnesium silicate Substances 0.000 claims abstract description 10
- 229910052919 magnesium silicate Inorganic materials 0.000 claims abstract description 10
- GSJMPHIKYICTQX-UHFFFAOYSA-N magnesium;oxosilicon Chemical compound [Mg].[Si]=O GSJMPHIKYICTQX-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000859 sublimation Methods 0.000 claims abstract description 9
- 230000008022 sublimation Effects 0.000 claims abstract description 9
- 239000002243 precursor Substances 0.000 claims abstract description 8
- 238000010574 gas phase reaction Methods 0.000 claims abstract description 7
- 238000009833 condensation Methods 0.000 claims abstract 2
- 230000005494 condensation Effects 0.000 claims abstract 2
- 239000000463 material Substances 0.000 claims description 43
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 35
- 229910052799 carbon Inorganic materials 0.000 claims description 35
- 239000007789 gas Substances 0.000 claims description 33
- 238000010438 heat treatment Methods 0.000 claims description 27
- 238000007740 vapor deposition Methods 0.000 claims description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000013078 crystal Substances 0.000 claims description 15
- 239000002131 composite material Substances 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 239000002210 silicon-based material Substances 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 9
- 229910004283 SiO 4 Inorganic materials 0.000 claims description 8
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 8
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 8
- 238000010902 jet-milling Methods 0.000 claims description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- 239000005977 Ethylene Substances 0.000 claims description 5
- 229910017625 MgSiO Inorganic materials 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract 1
- 238000005137 deposition process Methods 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 21
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 238000009826 distribution Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910052681 coesite Inorganic materials 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 229910052906 cristobalite Inorganic materials 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 229910052682 stishovite Inorganic materials 0.000 description 5
- 229910052905 tridymite Inorganic materials 0.000 description 5
- 150000002681 magnesium compounds Chemical class 0.000 description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000006978 adaptation Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052914 metal silicate Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 150000003376 silicon Chemical class 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 238000003991 Rietveld refinement Methods 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- SXFQCTMHFJARRW-UHFFFAOYSA-N acetylene;methane Chemical compound C.C#C SXFQCTMHFJARRW-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052839 forsterite Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 description 1
- 238000007431 microscopic evaluation Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000012764 semi-quantitative analysis Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
Classifications
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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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—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
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Silicon Compounds (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a silicon-based anode material for a lithium battery and a preparation method thereof, wherein a mixture of silicon, silicon dioxide and magnesium simple substance is subjected to pre-reaction under vacuum low temperature condition, then is subjected to high-temperature gas phase reaction under sublimation temperature, and meanwhile, a rear end collecting area is subjected to temperature regulation and control in a condensation deposition process to obtain a silicon oxide-magnesium silicate compound precursor.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a silicon-based negative electrode material for a lithium battery and a preparation method thereof.
Background
Under the situation that market demands are increasingly improved, research and development of graphite anode materials are close to theoretical values, breakthrough is difficult, silicon-based materials are widely researched in academia and industry because of the advantages of high theoretical capacity, rich resources, low lithium intercalation removal potential and the like, as one of the silicon-based materials, the silicon oxide materials have relatively small volume expansion in a circulation process and are more stable in circulation compared with the nano silicon materials, and the main problems of the silicon oxide materials include low conductivity and low first efficiency of the materials; at present, the modification research on the silicon oxide is also developed around the aspects, and main means comprise carbon coating, element doping, prelithiation and the like, and certain results are achieved in each research direction.
By introducing silicate materials into the traditional silicon oxide materials for dispersion distribution, the silicon oxide materials are modified to be used as silicon-based negative electrode materials, the silicate materials with dispersion distribution form a framework structure of the silicon-based negative electrode materials, the silicate framework can play a role in pinning facing the volume expansion of the silicon-based negative electrode, deformation stress is relieved, and the recycling performance of the materials is improved.
Patent CN108767241a discloses magnesium doped silicon oxide, preparation method and application in secondary lithium ion battery by mixing SiO x The gas contacts with metal Mg steam, and is co-deposited to obtain Mg doped silicon oxide, which is used as a cathode material of a lithium ion battery, and has high capacity and high initial coulombic efficiency.
In the existing doping scheme of the silicon-based material, lithium is pre-intercalated into SiO itself or pre-intercalated into the coated silicon oxide material, so that the Li source needs to react with the silicon-based material from the surface of SiO even through a carbon layer, a homogeneous result is difficult to form, and side reactions cannot be avoided, so that the performance of the final material is affected.
Researches show that oxygen in the silicon oxide can be combined with magnesium in advance through a magnesium thermal reaction, so that the consumption of lithium in the oxygen is reduced in the circulation process, the initial efficiency of a battery can be improved, the element doping is carried out in the front-end silicon oxide preparation process, the whole process is safer, the silicon grain size is controllable, the non-uniformity and the safety risk caused by the participation of a rear-end metal simple substance or metal hydride in the reaction are avoided, the front-end doping can simplify the process, the cost is reduced, and the large-scale production can be realized. However, the current magnesium pre-treatment technology is usually completed by using a solid phase reaction, and the magnesium thermal reduction reaction releases a large amount of heat, which is easy to cause the growth of silicon grains and affects the cycle life of the battery.
Disclosure of Invention
The invention aims to overcome the defects that the first coulombic efficiency of a silicon-based negative electrode material cannot be simultaneously met and the cycle performance is good in the prior art, and provides a silicon-based material for a lithium battery negative electrode and a preparation method thereof. The metal silicate in the silicon-based anode material prepared by the method is uniformly distributed, and the metal silicate has high initial discharge capacity, initial coulombic efficiency and high cycle performance when being applied to lithium ion batteries, and has high application value in the fields of electric automobiles, portable electric tools, household appliances and the like.
In order to achieve the above purpose, the invention is realized by the following technical scheme:
in one aspect, the present invention provides a silicon-based anode material for a lithium battery, the anode material comprising a silicon-based composite and a carbon layer coated on the surface of the silicon-based composite, the silicon-based composite comprising: silicon oxide (SiOx, 0<x.ltoreq.2) silicon (Si) grains, optionally MgSiO, present in the silicon oxide 3 Grain and Mg 2 SiO 4 And (5) crystal grains.
Preferably, in the silicon-based composite, mgSiO is added in an amount of 100% based on the total mass of the silicon-based composite 3 The mass ratio of the crystal grains is 2-48wt percent, mg 2 SiO 4 The mass ratio of the crystal grains is 0-6wt%, and the mass ratio of the silicon (Si) crystal grains is 0.5-30wt%; preferably, mgSiO 3 The mass ratio of the crystal grains is 5-25wt percent, mg 2 SiO 4 The mass ratio of the crystal grains is 0-4wt%, and the mass ratio of the silicon (Si) crystal grains is 4-15wt%.
Preferably, in the silicon-based anode material, the mass fraction of the carbon element is 2-8wt% based on 100% of the total mass of the silicon-based anode material, and it is understood by those skilled in the art that the carbon element is derived from a carbon layer coated on the surface of the silicon-based composite.
Preferably, in the silicon-based anode material, the carbon layer coated on the surface of the silicon-based composite may be coated in a conventional manner in the art, such as carbon deposition, and the average thickness of the coated carbon layer is 5-100nm, preferably the average thickness of the carbon layer is 10-20nm.
Preferably, in the silicon-based anode material, the silicon crystal grain size is 0-10nm, such as 1nm, 2nm, 3nm, 4nm, 5nm, 6nm, 7nm, 8nm, 9nm, wherein 0nm is not included.
Preferably, the specific surface area of the silicon-based anode material is 1-20m 2 /g, e.g. 2m 2 /g、4m 2 /g、8m 2 /g、12m 2 /g、16m 2 /g。
On the other hand, the invention also provides a preparation method of the silicon-based anode material for the lithium battery, which comprises the following steps:
(S1) weighing raw materials containing silicon, silicon dioxide and magnesium powder and mixing to obtain a mixture;
(S2) carrying out heat preservation treatment on the mixture obtained in the step (S1) under vacuum conditions;
(S3) heating the above-mentioned heat-insulating treatment mixture to a sublimation temperature while generating a magnesium source vapor and a silicon oxide vapor to perform a gas phase reaction;
(S4) condensing the gas phase mixture to precipitate a silicon oxide-magnesium silicate composite precursor;
(S5) jet milling the precipitated silicon oxide-magnesium silicate composite precursor;
(S6) carrying out vapor deposition on the crushed material of the silicon oxide-magnesium silicate precursor under the mixed gas atmosphere of carbon source gas and inert gas.
In the present invention, the molar ratio of silicon to silicon dioxide in step (S1) is 1:0.8-1:1.2, preferably 1:1-1.1:1; the content of the magnesium powder in the mixture is 1-16wt%, preferably 4-10%;
in the invention, the pressure of the heat preservation treatment under the vacuum condition in the step (S2) is 0.01-10Pa, the heat preservation temperature is 650-950 ℃, the heat preservation time is 1-8h, preferably the pressure of the vacuum heat preservation treatment is 0.01-5Pa, the heat preservation temperature is 700-900 ℃ and the heat preservation time is 3-6h.
In the invention, the sublimation temperature in the step (S3) is 1200-1400 ℃, the heating rate is 2-10 ℃/min, the gas phase reaction time is 10-20h, preferably the sublimation temperature is 1250-1350 ℃, the heating rate is 3-5 ℃/min, and the gas phase reaction time is 12-15h.
In the present invention, the condensing temperature in the step (S4) is 700 to 850℃and preferably 800 to 850 ℃.
In the present invention, the average particle diameter of the silicon oxide-magnesium silicate composite after pulverization in the step (S5) is 4 to 7. Mu.m.
In the invention, in the step (S6), the carbon source-containing gas is selected from one of methane, acetylene, ethylene and toluene; the inert gas is selected from one of nitrogen, argon and helium; the volume ratio of the carbon source gas in the mixed gas is 15-50%; the flow rate of the carbon source gas is 0.5-5L/min; the vapor deposition temperature is 800-950 ℃ and the constant temperature time is 0.5-5h; preferably, the volume ratio of the carbon source gas is 25-45%, the flow rate of the carbon source gas is 1-3L/min, the vapor deposition temperature is 850-900 ℃, and the constant temperature time is 1.5-3h.
The invention has the beneficial effects that:
in the preparation process of the magnesium-doped silicon oxide, the mixture of silicon, silicon dioxide and magnesium simple substance is pre-reacted in the vacuum low-temperature stage, so that on one hand, a stable magnesium compound can be generated to control the sublimation rate of the magnesium simple substance, the magnesium compound can be more uniformly doped into silicon oxide in the high-temperature vacuum reaction process, on the other hand, mgO can be more converted into magnesium silicate through the pre-reaction, and the simple substance magnesium with the same mole number can be combined with more oxygen, thereby improving the utilization rate of the simple substance magnesium, and finally improving the capacity and first effect of the modified silicon-based material. The lithium ion battery taking the modified silicon-based material as the negative electrode active material can simultaneously meet the requirements of high initial efficiency, high capacity and excellent cycle characteristics.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is an XRD pattern of a silicon-based modified anode material for lithium batteries obtained in example 1
FIG. 2 is a distribution spectrum of each element of the silicon-based modified anode material for lithium batteries obtained in example 1
Detailed Description
The invention will be further illustrated with reference to the following examples for a better understanding, but the embodiments of the invention are not limited thereto.
Raw materials and sources:
si powder is purchased from Hebei Tianjing new energy science and technology Co., ltd, the purity is 99.99%, and the granularity is 3-5 μm;
SiO 2 purchased from Jiangsu Lishi New Material Co., ltd., purity 99.9%, particle size 5-10 μm;
mg powder was purchased from shanxi fuhendy metal materials limited, purity: 99.99%, mesh number: 50-100 mesh.
Acetylene was purchased from tabacco torches gas Co., ltd, purity 99.9%
Other raw materials are all commercially available.
The following examples are given by way of illustration of detailed embodiments and specific procedures based on the technical scheme of the present invention, but the scope of the present invention is not limited to the following examples. The methods used in the examples described below are conventional methods unless otherwise specified.
Example 1
A silicon-based negative electrode material for a lithium battery and a preparation method thereof comprise the following steps:
(1) Mixing powder obtained by mixing Si and SiO2 in a molar ratio of 1:1 with Mg powder accounting for 6wt% of the mixture in a high-speed mixer to obtain a raw material mixture;
(2) Putting the raw material mixture into a vacuum high-temperature furnace, decompressing to below 10Pa, heating the equipment to 900 ℃ and performing heat treatment for 3 hours to obtain a first structural material;
(3) Continuously heating the obtained first structural material to 1350 ℃, keeping the temperature for 12 hours at a heating rate of 3 ℃/min, condensing the sublimated mixed gas on the inner wall of a collecting bin at 800 ℃ to obtain a second structural material;
(4) Jet milling the second structural material to obtain micro powder with an average particle size of about 6 μm;
(5) And (3) placing the obtained micron powder into a vapor deposition furnace for vapor deposition coating treatment, wherein the atmosphere condition is a mixed gas of nitrogen and acetylene, the acetylene accounts for 40%, the velocity of the acetylene is 1L/min, the vapor deposition temperature is 900 ℃, and the constant temperature time is 2h. And (3) cooling the sample to room temperature under the condition of nitrogen after coating by vapor deposition, and obtaining the silicon-based anode material for the lithium battery, wherein the carbon layer thickness of the silicon-based anode material is 15 nm.
The general distribution condition of Si, O and Mg elements in a sample can be seen through an energy spectrometer element distribution picture in FIG. 2, and the distribution uniformity of the Si, O and Mg elements in the material particles is better.
Example 2
A silicon-based negative electrode material for a lithium battery and a preparation method thereof comprise the following steps:
(1) Mixing powder obtained by mixing Si and SiO2 in a molar ratio of 1:0.8 with Mg powder accounting for 1wt% of the mixture in a high-speed mixer to obtain a raw material mixture;
(2) Putting the raw material mixture into a vacuum high-temperature furnace, decompressing to below 10Pa, heating the equipment to 800 ℃ and performing heat treatment for 4 hours to obtain a first structural material;
(3) Continuously heating the obtained first structural material to 1400 ℃, keeping the temperature for 10 hours at a heating rate of 2 ℃/min, condensing the sublimated mixed gas on the inner wall of a collecting bin at 850 ℃ to obtain a second structural material;
(4) Jet milling the second structural material to obtain micro powder with average particle size of about 7 μm;
(5) And (3) placing the obtained micron powder in a vapor deposition furnace for vapor deposition coating treatment, wherein the atmosphere condition is a mixed gas of argon and acetylene, the ratio of acetylene methane is 15%, the flow rate of the acetylene gas is 5L/min, the vapor deposition temperature is 950 ℃, and the constant temperature time is 0.5h. And (3) cooling the sample to room temperature under the condition of nitrogen after coating by vapor deposition, and obtaining the silicon-based anode material for the lithium battery, wherein the carbon layer thickness of the silicon-based anode material is 10 nm.
Example 3
A silicon-based negative electrode material for a lithium battery and a preparation method thereof comprise the following steps:
(1) Mixing powder obtained by mixing Si and SiO2 in a molar ratio of 1:1.2 with Mg powder accounting for 16% of the mixture in a high-speed mixer to obtain a raw material mixture;
(2) Putting the raw material mixture into a vacuum high-temperature furnace, decompressing to below 10Pa, heating the equipment to 950 ℃ and performing heat treatment for 1h to obtain a first structural material;
(3) Continuously heating the obtained first structural material to 1200 ℃, keeping the temperature for 20 hours at a heating rate of 10 ℃/min, condensing the sublimated mixed gas on the inner wall of a collecting bin at 800 ℃ to obtain a second structural material;
(4) Jet milling the second structural material to obtain micro powder with average particle size of about 4 μm;
(5) And (3) placing the obtained micron powder into a vapor deposition furnace for vapor deposition coating treatment, wherein the atmosphere condition is a mixed gas of helium and ethylene, the ethylene accounts for 50%, the ethylene gas flow rate is 0.5L/min, the vapor deposition temperature is 800 ℃, and the constant temperature time is 5h. And (3) cooling the sample to room temperature under the condition of nitrogen after coating by vapor deposition, and obtaining the silicon-based anode material for the lithium battery, wherein the carbon layer thickness of the silicon-based anode material is 5 nm.
Example 4
A silicon-based negative electrode material for a lithium battery and a preparation method thereof comprise the following steps:
(1) Mixing powder obtained by mixing Si and SiO2 in a molar ratio of 1:1.1 in a high-speed mixer with Mg powder accounting for 10% of the mixture to obtain a raw material mixture;
(2) Putting the raw material mixture into a vacuum high-temperature furnace, decompressing to below 10Pa, heating the equipment to 600 ℃ and performing heat treatment for 8 hours to obtain a first structural material;
(3) Continuously heating the obtained first structural material to 1300 ℃, keeping the temperature for 15 hours at a heating rate of 5 ℃/min, condensing the sublimated mixed gas on the inner wall of a collecting bin at 700 ℃ to obtain a second structural material;
(4) Jet milling the second structural material to obtain micro powder with an average particle size of about 5 μm;
(5) And (3) placing the obtained micron powder into a vapor deposition furnace for vapor deposition coating treatment, wherein the atmosphere condition is a mixed gas of argon and toluene, the toluene accounts for 45%, the toluene gas flow rate is 1.5L/min, the vapor deposition temperature is 900 ℃, and the constant temperature time is 2h. And (3) cooling the sample to room temperature under the condition of nitrogen after coating by vapor deposition, and obtaining the silicon-based anode material for the lithium battery, wherein the thickness of the carbon layer of the silicon-based anode material is 100 nm.
Example 5
A silicon-based negative electrode material for a lithium battery and a preparation method thereof comprise the following steps:
(1) Mixing powder obtained by mixing Si and SiO2 in a molar ratio of 1:1.1 in a high-speed mixer with Mg powder accounting for 10% of the mixture to obtain a raw material mixture;
(2) Putting the raw material mixture into a vacuum high-temperature furnace, decompressing to below 10Pa, heating the equipment to 900 ℃ and performing heat treatment for 3 hours to obtain a first structural material;
(3) Continuously heating the obtained first structural material to 1300 ℃, keeping the temperature for 15 hours at a heating rate of 5 ℃/min, condensing the sublimated mixed gas on the inner wall of a collecting bin at 850 ℃ to obtain a second structural material;
(4) Jet milling the second structural material to obtain micro powder with an average particle size of about 5 μm;
(5) And (3) placing the obtained micron powder into a vapor deposition furnace for vapor deposition coating treatment, wherein the atmosphere condition is a mixed gas of argon and toluene, the toluene accounts for 45%, the toluene gas flow rate is 1.5L/min, the vapor deposition temperature is 900 ℃, and the constant temperature time is 2h. And (3) cooling the sample to room temperature under the condition of nitrogen after coating by vapor deposition, and obtaining the silicon-based anode material for the lithium battery, wherein the thickness of the carbon layer of the silicon-based anode material is 100 nm.
Example 6
This example differs from example 1 above only in that the inner wall of the collection chamber in step (3) in example 1 above was set at 500 ℃.
Example 7
This example differs from example 1 above only in that the inner wall of the collection chamber in step (3) in example 1 above was set at 900 ℃.
Comparative example 1
This example differs from example 1 above only in that the heat treatment was not performed when the apparatus in step (2) of example 1 above was warmed to 900 ℃.
Comparative example 2
This example differs from example 1 above only in that the apparatus in step (2) of example 1 above was heated to 900 ℃ and heat treated for 9 hours.
The silicon-based negative electrode materials for lithium batteries prepared in examples 1 to 5 and comparative examples 1 to 4 were tested by the following methods:
the testing and characterization method comprises the following steps:
the X-ray diffraction was performed using a Germany (BRUKERD 8 ADVANCE) X-ray diffractometer, and the calculation of the grain size was determined based on the full width at half maximum (FWHM) of the diffraction peak of Si (110) in the X-ray diffraction measurement according to Sheller's equation (1), and XRD was performed in the 2 theta range of 10 to 90℃by using CuK alpha rays (for example, the wavelength of the light source: 1.5406 Angstrom).
C.S [ nm ] =K.lambda/B.cos θ. The general formula (1)
(in the general formula (1), k=0.9, λ=0.154 μm, b=half width (FWHM, rad), θ=peak position (angle)).
MgSiO 3 Content of (1) Mg 2 SiO 4 The content of MgSiO and the content of MgO in the silicon composite particles are respectively referred to as MgSiO 3 、Mg 2 SiO 4 And MgO content (wt%), each content was confirmed by XRD Rietveld refinement method.
The silicon content of the material was analyzed by ICP emission spectrometry, and the Si element content of the material was measured by Inductively Coupled Plasma (ICP) spectrometer model 7500ce, manufactured by Agilent company in the united states.
C content analysis was performed by an elemental analyzer, and the C content of the material was measured using a CS230 carbon sulfur analyzer produced by LECO company of America.
The material-coated carbon layer was subjected to nanoscale microscopic analysis by High Resolution Transmission Electron Microscopy (HRTEM), and the thickness of the carbon layer was measured using Tecnai G2F20 high resolution transmission electron microscopy, FEI company, usa.
The morphology of the material is observed by using a cold field emission scanning electron microscope (cold field emission scanning electron microscope) of Hitachi S-4800, and the composition and distribution of the elements are observed by combining an Oxford Oxford energy spectrometer (EDS) in the United kingdom, and the qualitative and semi-quantitative analysis of the elements is carried out by detecting the characteristic X-rays of each element.
The electrochemical cycle performance was tested using the following method: according to the cathode active material: sodium carboxymethyl cellulose (CMC): conductive carbon black (SP): styrene Butadiene Rubber (SBR) is mixed according to the mass ratio of 94.5:1.5:1.5:2.5 to prepare a working electrode, the working electrode is coated on a copper foil current collector, and the working electrode is dried in vacuum to prepare a negative electrode plate; then lithium sheet, 1mol/L LiPF 6 Electrolyte of three-component mixed solvent (mixed according to EC: DMC: emc=1:1:1 (v/v)), celgard2400 separator, housing were assembled into coin cells using conventional production process. The charge and discharge test of the button cell is carried out on a LAND cell test system of the Wuhan Jino electronic Co., ltd, and the charge and discharge voltage is limited to 0.05-1.5V, and the cycle performance test is carried out under normal temperature condition and 0.1C constant current charge and discharge.
The relevant performance data for examples 1-5 and comparative examples 1-4 are set forth in Table 1 below.
As is apparent from the above examples and comparative examples, the preparation methods provided in examples 1 to 4 control the sublimation rate of elemental magnesium by pre-reacting a mixture of silicon, silicon dioxide and elemental magnesium at a low temperature stage of vacuum to form a stable magnesium compound, so that it can be more uniformly incorporated into silicon oxide during a high temperature vacuum reaction. On the other hand, the product composition can be better controlled by controlling the temperature of the deposition area, so that the electrochemical performance of the final material is improved. The element distribution analysis is performed on the silicon-based anode material prepared in example 1 from fig. 2, and the result shows that C, si, mg, O elements in the prepared silicon-based anode material are uniformly distributed in the material, and the mixture of silicon, silicon dioxide and magnesium simple substance is not subjected to the pre-reaction in the vacuum low-temperature stage in comparative example 1 to generate a stable magnesium compound, so that the utilization rate of magnesium is low, and the capacity and first effect of the material are finally affected.
Comparative example 2 the mixture of silicon, silicon dioxide and elemental magnesium was pre-reacted for too long in the low temperature vacuum stage, which resulted in the formation of excess Mg2SiO4, thereby affecting the capacity and first effect of the material.
While the present invention has been described in detail through the foregoing description of the preferred embodiment, it should be understood that the foregoing description is not to be considered as limiting the invention. Those skilled in the art will appreciate that certain modifications and adaptations of the invention are possible and can be made under the teaching of the present specification. Such modifications and adaptations are intended to be within the scope of the present invention as defined in the appended claims.
Claims (10)
1. A silicon-based negative electrode material for a lithium battery, characterized in that the negative electrode material comprises a silicon-based compound and a carbon layer coated on the surface of the silicon-based compound, the silicon-based compound comprising: silicon oxide (SiOx, 0<x.ltoreq.2) silicon (Si) grains, mgSiO, present in the silicon oxide 3 Grains and optionally Mg 2 SiO 4 And (5) crystal grains.
2. The silicon-based anode material according to claim 1, wherein MgSiO is contained in the silicon-based composite in an amount of 100% by weight based on the total mass of the silicon-based composite 3 The mass ratio of the crystal grains is 2-48wt percent, mg 2 SiO 4 The mass ratio of the crystal grains is 0-6wt%, and the mass ratio of the silicon (Si) crystal grains is 0.5-30wt%; preferably, mgSiO 3 The mass ratio of the crystal grains is 5-25wt percent, mg 2 SiO 4 The mass ratio of the crystal grains is 0-4wt%, and the mass ratio of the silicon (Si) crystal grains isThe ratio is 4-15wt%.
3. The silicon-based anode material according to claim 1 or 2, wherein the mass fraction of carbon element of the surface-coated carbon layer in the silicon-based anode material is 2 to 8wt% relative to the silicon-based anode material; and/or the average thickness of the coated carbon layer is 5-100nm, preferably the average thickness of the carbon layer is 10-20nm.
4. A silicon-based anode material according to any one of claims 1 to 3, wherein the silicon grain size is 0 to 10nm excluding 0nm; and/or the specific surface area of the silicon-based anode material is 1-20m 2 /g。
5. The method for producing a silicon-based anode material according to any one of claims 1 to 4, comprising the steps of:
(S1) weighing raw materials containing silicon, silicon dioxide and magnesium powder and mixing to obtain a mixture;
(S2) carrying out heat preservation treatment on the mixture obtained in the step (S1) under vacuum conditions;
(S3) heating the above-mentioned heat-insulating treatment mixture to a sublimation temperature while generating a magnesium source vapor and a silicon oxide vapor to perform a gas phase reaction;
(S4) condensing the gas phase mixture to precipitate a silicon oxide-magnesium silicate composite precursor;
(S5) jet milling the precipitated silicon oxide-magnesium silicate composite precursor;
(S6) carrying out vapor deposition on the crushed material of the silicon oxide-magnesium silicate precursor under the mixed gas atmosphere of carbon source gas and inert gas.
6. The process according to claim 5, wherein the molar ratio of silicon to silicon dioxide in step (S1) is from 1:0.8 to 1:1.2, preferably from 1:1 to 1.1:1; and/or the magnesium powder is contained in the mixture in an amount of 1 to 20wt%, preferably 6 to 10wt%.
7. The method according to claim 5 or 6, wherein the pressure of the heat-retaining treatment under the vacuum condition in the step (S2) is 0.01 to 10Pa, the heat-retaining temperature is 650 to 950 ℃ and the heat-retaining time is 1 to 8 hours, preferably the pressure of the vacuum heat-retaining treatment is 0.01 to 5Pa, the heat-retaining temperature is 700 to 900 ℃ and the heat-retaining time is 3 to 6 hours.
8. The preparation method according to any one of claims 5 to 7, wherein the sublimation temperature in step (S3) is 1200 to 1400 ℃, the heating rate is 2 to 10 ℃/min, and/or the time of the gas phase reaction is 10 to 20 hours, preferably the sublimation temperature is 1250 to 1350 ℃, the heating rate is 3 to 5 ℃/min, and/or the time of the gas phase reaction is 12 to 15 hours.
9. The preparation process according to any one of claims 5 to 8, wherein the condensation temperature in step (S4) is 700-850 ℃, preferably 800-850 ℃; and/or, the average particle diameter of the silicon oxide-magnesium silicate precursor after pulverization in the step (S5) is 4-7 μm.
10. The production method according to any one of claims 5 to 9, wherein the carbon-containing source gas in step (S6) is selected from one of methane, acetylene, ethylene, toluene; and/or the inert gas is selected from one of nitrogen, argon and helium; and/or the volume ratio of the carbon source gas in the mixed gas is 15-50%; the flow rate of the carbon source gas is 0.5-5L/min; and/or the vapor deposition temperature is 800-950 ℃ and the constant temperature time is 0.5-5h; preferably, the volume ratio of the carbon source gas is 25-45%, the flow rate of the carbon source gas is 1-3L/min, the vapor deposition temperature is 850-900 ℃, and the constant temperature time is 1.5-3h.
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