CN115159527B - Hard carbon coated silicon nanoparticle composite microsphere negative electrode material and preparation method and application thereof - Google Patents
Hard carbon coated silicon nanoparticle composite microsphere negative electrode material and preparation method and application thereof Download PDFInfo
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- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 94
- 239000005543 nano-size silicon particle Substances 0.000 title claims abstract description 86
- 239000002131 composite material Substances 0.000 title claims abstract description 63
- 239000004005 microsphere Substances 0.000 title claims abstract description 62
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 58
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000010405 anode material Substances 0.000 claims abstract description 32
- 238000001035 drying Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 238000007789 sealing Methods 0.000 claims abstract description 12
- 239000005049 silicon tetrachloride Substances 0.000 claims abstract description 12
- 238000004729 solvothermal method Methods 0.000 claims abstract description 12
- 239000007833 carbon precursor Substances 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 28
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 7
- 229910001416 lithium ion Inorganic materials 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 4
- 125000002534 ethynyl group Chemical group [H]C#C* 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
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 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
- 229910052757 nitrogen 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
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 3
- 229920000767 polyaniline Polymers 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- 239000011149 active material Substances 0.000 claims description 2
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 22
- 229910052710 silicon Inorganic materials 0.000 abstract description 22
- 239000010703 silicon Substances 0.000 abstract description 22
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052744 lithium Inorganic materials 0.000 abstract description 6
- 239000003792 electrolyte Substances 0.000 abstract description 5
- 238000006138 lithiation reaction Methods 0.000 abstract description 5
- 239000000047 product Substances 0.000 description 32
- 238000001816 cooling Methods 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000004321 preservation Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000013543 active substance Substances 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 238000007709 nanocrystallization Methods 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- 239000011870 silicon-carbon composite anode material Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
- C01B33/021—Preparation
- C01B33/027—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
-
- 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
- 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
- H01M4/62—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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- 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a hard carbon coated silicon nanoparticle composite microsphere negative electrode material and a preparation method and application thereof, wherein the preparation method comprises the following steps: dissolving silicon tetrachloride and a hard carbon precursor in an alcohol solvent to form a mixed solution; pouring the mixed solution into a hydrothermal reaction kettle for sealing, and putting the hydrothermal reaction kettle into a baking oven for heating to perform solvothermal reaction to obtain a reaction product; and drying the reaction product, and calcining in an inert atmosphere and/or a reducing atmosphere to obtain the hard carbon coated silicon nanoparticle composite microsphere anode material. In the invention, the hard carbon spheres can buffer the volume expansion in the lithiation process of silicon, the silicon nano particles are wrapped by the hard carbon spheres, so that the silicon nano particles are prevented from being in direct contact with electrolyte, the first coulombic efficiency of the nano silicon anode material is improved, the active lithium loss caused by continuous growth of SEI in the circulation process is reduced, and the circulation stability is obviously improved; in addition, the conductivity of the hard carbon spheres is better than that of the silicon anode material, and the multiplying power performance of the silicon anode material is greatly improved.
Description
Technical Field
The invention relates to the technical field of negative electrode materials, in particular to a hard carbon coated silicon nanoparticle composite microsphere negative electrode material, and a preparation method and application thereof.
Background
The silicon anode material is expected to replace a graphite anode material with wide commercial application due to the advantages of high capacity, low lithium intercalation and deintercalation potential, environmental friendliness, abundant reserves, low cost and the like. However, there is a serious volume expansion in the lithiation process of the silicon negative electrode, resulting in crushing and pulverization of silicon particles, exposure of more surfaces, continuous growth of SEI film, consumption of active lithium ions, and serious deterioration of cycle performance. The loss of electrical connection after particle breakage and the thicker SEI film can lead to the increase of the internal resistance of the battery cell, and the cycle and the dynamic performance of the battery cell are deteriorated. Meanwhile, the conductivity of the silicon anode material is lower than that of the graphite anode material, and the multiplying power performance of the battery cell is severely limited.
The nanocrystallization of the silicon anode material, the compounding with the carbon material and the use of the oxide of silicon are common means for improving the volume expansion, so that the volume expansion can be relieved to a certain extent, but the problems of low initial coulombic efficiency, low energy density and the like are easily introduced, and the improvement effect is often inferior to expectations.
Accordingly, the prior art is still in need of improvement and development.
Disclosure of Invention
In view of the defects in the prior art, the invention aims to provide a hard carbon coated silicon nanoparticle composite microsphere negative electrode material, and a preparation method and application thereof, and aims to solve the problems that the existing silicon negative electrode material is easy to expand in volume, and the cycle performance, the dynamic performance and the multiplying power performance of a battery cell are poor.
The technical scheme of the invention is as follows:
the preparation method of the hard carbon coated silicon nanoparticle composite microsphere negative electrode material comprises the following steps:
dissolving silicon tetrachloride and a hard carbon precursor in an alcohol solvent to form a mixed solution;
pouring the mixed solution into a hydrothermal reaction kettle for sealing, and putting the hydrothermal reaction kettle into an oven for heating to perform solvothermal reaction to obtain a reaction product;
and drying the reaction product, and calcining in an inert atmosphere and/or a reducing atmosphere to obtain the hard carbon coated silicon nanoparticle composite microsphere anode material.
The hard carbon precursor is one or more of glucose, sucrose, a phenolic resin precursor solution, a urea-formaldehyde resin precursor solution, polyacrylonitrile, polyaniline, furfural and furfuryl alcohol.
The preparation method of the hard carbon coated silicon nanoparticle composite microsphere negative electrode material comprises the step of preparing an alcohol solvent from one or more of ethanol, propanol, isopropanol and butanol.
The preparation method of the hard carbon coated silicon nanoparticle composite microsphere negative electrode material comprises the step of putting the hydrothermal reaction kettle into a baking oven to be heated for solvothermal reaction, wherein the solvothermal reaction temperature is 120-200 ℃ and the solvothermal reaction time is 2-10h.
The preparation method of the hard carbon coated silicon nanoparticle composite microsphere anode material comprises the steps of drying the reaction product, and calcining in an inert atmosphere and/or a reducing atmosphere at 600-1800 ℃ for 0.5-10h.
The preparation method of the hard carbon coated silicon nanoparticle composite microsphere negative electrode material comprises the following steps of wherein the inert atmosphere is one or more of nitrogen, argon and helium; and/or the reducing atmosphere is one or two of acetylene and hydrogen.
The invention relates to a hard carbon coated silicon nanoparticle composite microsphere negative electrode material, which is prepared by adopting a preparation method of the hard carbon coated silicon nanoparticle composite microsphere negative electrode material.
The hard carbon coated silicon nanoparticle composite microsphere negative electrode material comprises a hard carbon sphere and silicon nanoparticles embedded in the hard carbon sphere.
The hard carbon coated silicon nanoparticle composite microsphere negative electrode material comprises the hard carbon coated silicon nanoparticle composite microsphere negative electrode material, wherein the diameter of the hard carbon coated silicon nanoparticle composite microsphere negative electrode material is 0.5-5 mu m, the particle size of the silicon nanoparticle is 5-50nm, and the hard carbon spheres account for 20-90% of the hard carbon coated silicon nanoparticle composite microsphere negative electrode material by mass ratio.
The application of the hard carbon coated silicon nanoparticle composite microsphere negative electrode material comprises the step of using the hard carbon coated silicon nanoparticle composite microsphere negative electrode material as an active substance on a lithium ion battery negative electrode plate.
The beneficial effects are that: the invention provides a preparation method of a hard carbon coated silicon nanoparticle composite microsphere negative electrode material. Compared with the prior art, the silicon exists in the form of nano particles with the size less than 50nm, the volume expansion is obviously improved, and meanwhile, the hard carbon spheres can buffer the volume expansion in the lithiation process of the silicon; the silicon nano particles are wrapped by the hard carbon spheres, so that the silicon nano particles are prevented from being in direct contact with electrolyte, the first coulombic efficiency of the nano silicon anode material is improved, the active lithium loss caused by continuous growth of SEI in the circulation process is reduced, and the circulation stability is obviously improved; in addition, the conductivity of the hard carbon spheres is better than that of the silicon anode material, and the multiplying power performance of the silicon anode material is greatly improved.
Drawings
FIG. 1 is a flowchart of a method for preparing a hard carbon coated silicon nanoparticle composite microsphere negative electrode material according to a preferred embodiment of the present invention.
Fig. 2 is an SEM image of a hard carbon coated silicon nanoparticle composite microsphere negative electrode material prepared in example 1 of the present invention.
Fig. 3 is a TEM image of a hard carbon coated silicon nanoparticle composite microsphere negative electrode material prepared in example 1 of the present invention.
Detailed Description
The invention provides a hard carbon coated silicon nanoparticle composite microsphere negative electrode material, a preparation method and application thereof, and aims to make the purposes, the technical scheme and the effects of the invention clearer and more definite. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The invention provides a preparation method of a hard carbon coated silicon nanoparticle composite microsphere anode material, which is shown in figure 1 and comprises the following steps:
s10, dissolving silicon tetrachloride and a hard carbon precursor in an alcohol solvent to form a mixed solution;
s20, pouring the mixed solution into a hydrothermal reaction kettle for sealing, and putting the hydrothermal reaction kettle into an oven for heating to perform solvothermal reaction to obtain a reaction product;
and S30, drying the reaction product, and calcining in an inert atmosphere and/or a reducing atmosphere to obtain the hard carbon coated silicon nanoparticle composite microsphere anode material.
The invention provides a simple, efficient and easy-to-operate method for preparing a hard carbon coated silicon nanoparticle composite microsphere negative electrode material. In the invention, the silicon nano particles can exist in a size form with the particle size smaller than 50nm, the volume expansion is obviously improved, and meanwhile, the hard carbon spheres can buffer the volume expansion in the silicon lithiation process; the silicon nano particles are wrapped by the hard carbon spheres, so that the silicon nano particles are prevented from being in direct contact with electrolyte, the first coulombic efficiency of the nano silicon anode material is improved, the active lithium loss caused by continuous growth of SEI in the circulation process is reduced, and the circulation stability is obviously improved; in addition, the conductivity of the hard carbon spheres is better than that of the silicon anode material, and the multiplying power performance of the silicon anode material is greatly improved.
In some embodiments, the hard carbon precursor may be one or more of any carbon-containing compounds that generate spherical hard carbon precursors at high temperature and high pressure, such as, but not limited to, one or more of glucose, sucrose, phenolic resin precursor solution, urea resin precursor solution, polyacrylonitrile, polyaniline, furfural, and furfuryl alcohol.
In some embodiments, the alcoholic solvent is one or more of ethanol, propanol, isopropanol, and butanol, but is not limited thereto.
In some embodiments, the hydrothermal reaction kettle is placed in an oven to be heated for solvothermal reaction, wherein the solvothermal reaction temperature is 120-200 ℃, such as 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃ and the like; the solvothermal reaction time is 2 to 10 hours, and may be, for example, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, etc. Preferably, the solvothermal reaction is carried out at a temperature of 140-60 ℃ for a period of 4-6 hours.
In some embodiments, the step of calcining the reaction product in an inert and/or reducing atmosphere after drying the reaction product may be performed at a temperature of 600-1800 ℃, for example 600 ℃, 800 ℃, 1000 ℃, 1200 ℃, 1400 ℃, 1500 ℃, 1600 ℃, 1700 ℃, 1800 ℃, etc.; the calcination treatment time is 0.5 to 10 hours, and may be, for example, 0.5 hours, 2 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, etc. Preferably, the calcination treatment is carried out at a temperature of 800200 ℃ for a time of 1-3 hours.
In some embodiments, the calcination treatment may be performed under an inert atmosphere alone or under a reducing atmosphere, or may be performed under a mixed atmosphere of an inert atmosphere and a reducing atmosphere. In this embodiment, the inert atmosphere is one or more of nitrogen, argon and helium; the reducing atmosphere is one or two of acetylene and hydrogen.
In some specific embodiments, when the calcination treatment is performed under a mixed atmosphere of an inert atmosphere and a reducing atmosphere, the volume ratio of the inert atmosphere to the reducing atmosphere is 90-95:5-10. In the volume ratio range, the calcining treatment efficiency is higher, and the hard carbon coated silicon nanoparticle composite microsphere anode material with better multiplying power performance and higher cycle capacity retention rate can be prepared. For example, the mixed atmosphere may be argon and acetylene with a volume ratio of 90:10, or argon and hydrogen with a volume ratio of 95:5.
In some embodiments, a hard carbon coated silicon nanoparticle composite microsphere negative electrode material is also provided, wherein the hard carbon coated silicon nanoparticle composite microsphere negative electrode material is prepared by the preparation method of the hard carbon coated silicon nanoparticle composite microsphere negative electrode material. In this embodiment, the hard carbon coated silicon nanoparticle composite microsphere negative electrode material is composed of a hard carbon sphere and silicon nanoparticles embedded in the hard carbon sphere, wherein the diameter of the hard carbon coated silicon nanoparticle composite microsphere negative electrode material is 0.5-5 μm, the particle diameter of the silicon nanoparticles is 5-50nm, and the hard carbon sphere accounts for 20-90% of the mass ratio of the hard carbon coated silicon nanoparticle composite microsphere negative electrode material.
In some embodiments, the application of the hard carbon coated silicon nanoparticle composite microsphere negative electrode material is also provided, and the hard carbon coated silicon nanoparticle composite microsphere negative electrode material is used as an active substance on a negative electrode plate of a lithium ion battery. In the invention, as the silicon nano particles in the hard carbon coated silicon nano particle composite microsphere negative electrode material can exist in a size form that the particle size is smaller than 50nm, the volume expansion is obviously improved, and meanwhile, the hard carbon spheres can buffer the volume expansion in the silicon lithiation process; the silicon nano particles are wrapped by the hard carbon spheres, so that the silicon nano particles can be prevented from being in direct contact with electrolyte, the first coulombic efficiency of the nano silicon anode material is improved, the active lithium loss caused by continuous growth of SEI in the circulation process is reduced, and the circulation stability is obviously improved; in addition, the conductivity of the hard carbon spheres is better than that of the silicon anode material, and the multiplying power performance of the silicon anode material is greatly improved. Therefore, after the hard carbon coated silicon nanoparticle composite microsphere negative electrode material is used as an active substance on a negative electrode plate of a lithium ion battery, the prepared lithium ion battery has better multiplying power performance, higher first coulombic efficiency and higher cycle capacity retention rate.
The invention is further illustrated by the following examples:
example 1
1.2g of silicon tetrachloride and 2.0g of furfural were weighed and dissolved in 80mL of ethanol, and stirred on a magnetic stirrer for 2 hours, so that the solutions were uniformly mixed. Transferring the solution into a 100mL inner container of a hydrothermal reaction kettle, and then placing the hydrothermal reaction kettle into the hydrothermal reaction kettle, and sealing by a cover. And (3) placing the hydrothermal reaction kettle into a baking oven at 140 ℃ for heat preservation for 10 hours, and naturally cooling the hydrothermal reaction kettle to room temperature after the reaction is completed. Taking out the precipitated product in the hydrothermal reaction kettle, respectively cleaning the precipitated product with deionized water and ethanol solution for three times, and putting the washed product into a vacuum oven at 80 ℃ for drying for 12 hours. And (3) placing the dried product into a tubular furnace, heating to 800 ℃ in Ar atmosphere, preserving heat for 1h at 800 ℃, and naturally cooling to room temperature to obtain the hard carbon coated silicon nanoparticle composite microsphere anode material.
Example 2
1.5g of silicon tetrachloride and 2.0g of furfural were weighed and dissolved in 80mL of ethanol, and stirred on a magnetic stirrer for 2 hours, so that the solutions were uniformly mixed. Transferring the solution into a 100mL inner container of a hydrothermal reaction kettle, and then placing the hydrothermal reaction kettle into the hydrothermal reaction kettle, and sealing by a cover. And (3) placing the hydrothermal reaction kettle into a baking oven at 140 ℃ for heat preservation for 10 hours, and naturally cooling the hydrothermal reaction kettle to room temperature after the reaction is completed. Taking out the precipitated product in the hydrothermal reaction kettle, respectively cleaning the precipitated product with deionized water and ethanol solution for three times, and putting the washed product into a vacuum oven at 80 ℃ for drying for 12 hours. And (3) placing the dried product into a tubular furnace, heating to 800 ℃ in Ar atmosphere, preserving heat for 1h at 800 ℃, and naturally cooling to room temperature to obtain the hard carbon coated silicon nanoparticle composite microsphere anode material.
Example 3
1.8g of silicon tetrachloride and 2.0g of furfural were weighed and dissolved in 80mL of ethanol, and stirred on a magnetic stirrer for 2 hours, so that the solutions were uniformly mixed. Transferring the solution into a 100mL inner container of a hydrothermal reaction kettle, and then placing the hydrothermal reaction kettle into the hydrothermal reaction kettle, and sealing by a cover. And (3) placing the hydrothermal reaction kettle into a baking oven at 140 ℃ for heat preservation for 10 hours, and naturally cooling the hydrothermal reaction kettle to room temperature after the reaction is completed. Taking out the precipitated product in the hydrothermal reaction kettle, respectively cleaning the precipitated product with deionized water and ethanol solution for three times, and putting the washed product into a vacuum oven at 80 ℃ for drying for 12 hours. And (3) placing the dried product into a tubular furnace, heating to 800 ℃ in Ar atmosphere, preserving heat for 1h at 800 ℃, and naturally cooling to room temperature to obtain the hard carbon coated silicon nanoparticle composite microsphere anode material.
Example 4
1.2g of silicon tetrachloride and 2.4g of furfural were weighed and dissolved in 80mL of ethanol, and stirred on a magnetic stirrer for 2 hours, so that the solutions were uniformly mixed. Transferring the solution into a 100mL inner container of a hydrothermal reaction kettle, and then placing the hydrothermal reaction kettle into the hydrothermal reaction kettle, and sealing by a cover. And (3) placing the hydrothermal reaction kettle into a baking oven at 140 ℃ for heat preservation for 10 hours, and naturally cooling the hydrothermal reaction kettle to room temperature after the reaction is completed. Taking out the precipitated product in the hydrothermal reaction kettle, respectively cleaning the precipitated product with deionized water and ethanol solution for three times, and putting the washed product into a vacuum oven at 80 ℃ for drying for 12 hours. And (3) placing the dried product into a tubular furnace, heating to 800 ℃ in Ar atmosphere, preserving heat for 1h at 800 ℃, and naturally cooling to room temperature to obtain the hard carbon coated silicon nanoparticle composite microsphere anode material.
Example 5
1.2g of silicon tetrachloride and 2.0g of furfural were weighed and dissolved in 80mL of ethanol, and stirred on a magnetic stirrer for 2 hours, so that the solutions were uniformly mixed. Transferring the solution into a 100mL inner container of a hydrothermal reaction kettle, and then placing the hydrothermal reaction kettle into the hydrothermal reaction kettle, and sealing by a cover. And (3) placing the hydrothermal reaction kettle into a 160 ℃ oven for heat preservation for 10 hours, and naturally cooling the hydrothermal reaction kettle to room temperature after the reaction is completed. Taking out the precipitated product in the hydrothermal reaction kettle, respectively cleaning the precipitated product with deionized water and ethanol solution for three times, and putting the washed product into a vacuum oven at 80 ℃ for drying for 12 hours. And (3) placing the dried product into a tubular furnace, heating to 800 ℃ in Ar atmosphere, preserving heat for 1h at 800 ℃, and naturally cooling to room temperature to obtain the hard carbon coated silicon nanoparticle composite microsphere anode material.
Example 6
1.2g of silicon tetrachloride and 2.0g of furfural were weighed and dissolved in 80mL of ethanol, and stirred on a magnetic stirrer for 2 hours, so that the solutions were uniformly mixed. Transferring the solution into a 100mL inner container of a hydrothermal reaction kettle, and then placing the hydrothermal reaction kettle into the hydrothermal reaction kettle, and sealing by a cover. And (3) placing the hydrothermal reaction kettle into a 160 ℃ oven for heat preservation for 10 hours, and naturally cooling the hydrothermal reaction kettle to room temperature after the reaction is completed. Taking out the precipitated product in the hydrothermal reaction kettle, respectively cleaning the precipitated product with deionized water and ethanol solution for three times, and putting the washed product into a vacuum oven at 80 ℃ for drying for 12 hours. And (3) placing the dried product in a tubular furnace, heating to 800 ℃ in a mixed atmosphere consisting of Ar and hydrogen in a volume ratio of 95:5, preserving heat at 1000 ℃ for 1h, and naturally cooling to room temperature to obtain the hard carbon coated silicon nanoparticle composite microsphere anode material.
Comparative example 1
1.2g of silicon tetrachloride and 1g of conductive carbon black are weighed and placed in 80mL of ethanol, and the mixture is subjected to ultrasonic dispersion for 30min to form a uniformly dispersed suspension. Transferring the suspension into a 100mL inner container of a hydrothermal reaction kettle, and then placing the hydrothermal reaction kettle into the hydrothermal reaction kettle, and sealing by a cover. And (3) placing the hydrothermal reaction kettle into a baking oven at 140 ℃ for heat preservation for 10 hours, and naturally cooling the hydrothermal reaction kettle to room temperature after the reaction is completed. Taking out the precipitated product in the hydrothermal reaction kettle, respectively cleaning the precipitated product with deionized water and ethanol solution for three times, and putting the washed product into a vacuum oven at 80 ℃ for drying for 12 hours. And (3) placing the dried product into a tubular furnace, heating to 800 ℃ in Ar atmosphere, preserving heat for 1h at 800 ℃, and naturally cooling to room temperature to obtain the silicon-carbon composite anode material.
Comparative example 2
1.2g of silicon tetrachloride was weighed and dissolved in 80mL of ethanol, and stirred on a magnetic stirrer for 2 hours to mix the solution uniformly. Transferring the solution into a 100mL inner container of a hydrothermal reaction kettle, and then placing the hydrothermal reaction kettle into the hydrothermal reaction kettle, and sealing by a cover. And (3) placing the hydrothermal reaction kettle into a baking oven at 140 ℃ for heat preservation for 10 hours, and naturally cooling the hydrothermal reaction kettle to room temperature after the reaction is completed. Taking out the precipitated product in the hydrothermal reaction kettle, respectively cleaning the precipitated product with deionized water and ethanol solution for three times, and putting the washed product into a vacuum oven at 80 ℃ for drying for 12 hours. And (3) placing the dried product into a tubular furnace, heating to 800 ℃ in Ar atmosphere, preserving heat for 1h at 800 ℃, and naturally cooling to room temperature to obtain the nano silicon anode material.
The hard carbon coated silicon nanoparticle composite microsphere negative electrode material prepared in the above example 1 is subjected to structural and morphological characterization: the morphology features are observed by adopting a Scanning Electron Microscope (SEM) and a Transmission Electron Microscope (TEM), and the carbon content in the composite material is characterized by thermogravimetric testing. As shown in fig. 2 and 3, it can be seen from fig. 2 that the sample prepared in example 1 is spherical particles with a particle size of about 1 micron; as can be seen from fig. 3, the sample prepared in example 1 has a large number of black nanoparticles embedded therein, and HRTEM results indicate that the black particles are silicon nanoparticles.
The negative electrode material assemblies prepared in examples 1-6 and comparative examples 1-2 were assembled and buckled for electrical property characterization: negative electrode material, conductive carbon black and binder polyacrylic acid (PAA, 25% aqueous solution) were mixed according to 80:10: mixing at 10 ratio, grinding thoroughly, dispersing on a homogenizer for 15min to obtain viscous active material slurry. And uniformly coating the slurry on the copper foil by adopting a knife coating method, and transferring the coated negative electrode plate into a vacuum oven at 80 ℃ for drying for 12 hours. The dried pole piece is rolled, punched into a round pole piece with the diameter of 12mm and weighed. Immediately transferring the weighed pole piece into a glove box protected by Ar atmosphere for assembling CR2016 type buckle, wherein the electrolyte is 1mol/L LiPF 6 Dissolved in EC: dec=1:1 (volume ratio), 10% fec was added in volume ratio, metallic lithium sheet as negative electrode, celgard2300 as separator. The LAND battery test system is adopted for carrying out the buckling charge and discharge test, the charge and discharge voltage range is 0.001-2V, and the measured results are shown in Table 1:
table 1 electrical characterization results
As can be seen from the data in Table 1, the hard carbon coated silicon nanoparticle composite microsphere negative electrode material provided by the invention can remarkably improve the cycling stability of the silicon negative electrode material although the gram capacity of the silicon negative electrode is reduced, so that the silicon negative electrode material can still maintain higher gram capacity in the later period of cycling. Meanwhile, the problems of initial coulombic efficiency, rate capability and the like can be improved, and the requirement of the lithium ion battery on high-performance anode materials is met.
It is to be understood that the invention is not limited in its application to the examples described above, but is capable of modification and variation in light of the above teachings by those skilled in the art, and that all such modifications and variations are intended to be included within the scope of the appended claims.
Claims (5)
1. The preparation method of the hard carbon coated silicon nanoparticle composite microsphere negative electrode material is characterized by comprising the following steps of:
dissolving silicon tetrachloride and a hard carbon precursor in an alcohol solvent to form a mixed solution;
pouring the mixed solution into a hydrothermal reaction kettle for sealing, and putting the hydrothermal reaction kettle into an oven for heating to perform solvothermal reaction to obtain a reaction product;
drying the reaction product, and calcining the reaction product in a mixed atmosphere of an inert atmosphere and a reducing atmosphere, wherein the volume ratio of the inert atmosphere to the reducing atmosphere is 90-95:5-10, so as to obtain a hard carbon coated silicon nanoparticle composite microsphere anode material; the hard carbon coated silicon nanoparticle composite microsphere negative electrode material consists of hard carbon spheres and silicon nanoparticles embedded in the hard carbon spheres, wherein the diameter of the hard carbon coated silicon nanoparticle composite microsphere negative electrode material is 0.6-1 mu m, the particle size of the silicon nanoparticles is 15-20nm, and the mass ratio of the hard carbon spheres to the hard carbon coated silicon nanoparticle composite microsphere negative electrode material is 40.9-66.8%;
the temperature of the calcination treatment is 800-1000 ℃ and the time is 1h;
the inert atmosphere is one or more of nitrogen, argon and helium;
the reducing atmosphere is one or two of acetylene and hydrogen;
the temperature of the solvothermal reaction is 140-160 ℃ and the time is 2-10h.
2. The method for preparing the hard carbon coated silicon nanoparticle composite microsphere negative electrode material according to claim 1, wherein the hard carbon precursor is one or more of glucose, sucrose, a phenolic resin precursor solution, a urea formaldehyde resin precursor solution, polyacrylonitrile, polyaniline, furfural and furfuryl alcohol.
3. The method for preparing the hard carbon coated silicon nanoparticle composite microsphere negative electrode material according to claim 1, wherein the alcohol solvent is one or more of ethanol, propanol, isopropanol and butanol.
4. The hard carbon coated silicon nanoparticle composite microsphere negative electrode material is characterized by being prepared by adopting the preparation method of the hard carbon coated silicon nanoparticle composite microsphere negative electrode material in any one of claims 1-3, wherein the hard carbon coated silicon nanoparticle composite microsphere negative electrode material consists of hard carbon spheres and silicon nanoparticles embedded in the hard carbon spheres, the diameter of the hard carbon coated silicon nanoparticle composite microsphere negative electrode material is 0.6-1 mu m, the particle diameter of the silicon nanoparticles is 15-20nm, and the mass ratio of the hard carbon spheres to the hard carbon coated silicon nanoparticle composite microsphere negative electrode material is 40.9-66.8%.
5. The use of the hard carbon coated silicon nanoparticle composite microsphere negative electrode material according to claim 4, wherein the hard carbon coated silicon nanoparticle composite microsphere negative electrode material is used as an active material on a negative electrode plate of a lithium ion battery.
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