CN116544397A - Carbon-coated metal fluoride modified silicon anode material and preparation method and application thereof - Google Patents
Carbon-coated metal fluoride modified silicon anode material and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 27
- 229910001512 metal fluoride Inorganic materials 0.000 title claims abstract description 22
- 239000010405 anode material Substances 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000002131 composite material Substances 0.000 claims abstract description 34
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000243 solution Substances 0.000 claims abstract description 27
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 150000003376 silicon Chemical class 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- 239000010410 layer Substances 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 229910017855 NH 4 F Inorganic materials 0.000 claims abstract description 6
- 239000007983 Tris buffer Substances 0.000 claims abstract description 6
- 239000011247 coating layer Substances 0.000 claims abstract description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 6
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000012456 homogeneous solution Substances 0.000 claims abstract description 3
- 230000001681 protective effect Effects 0.000 claims abstract description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 21
- 229910001416 lithium ion Inorganic materials 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 8
- 239000013067 intermediate product Substances 0.000 claims description 7
- 239000007773 negative electrode material Substances 0.000 claims description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 5
- 239000000919 ceramic Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 239000011863 silicon-based powder Substances 0.000 claims description 5
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 4
- 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
- 239000008103 glucose Substances 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 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 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 230000005518 electrochemistry Effects 0.000 abstract description 2
- 229910008449 SnF 2 Inorganic materials 0.000 description 10
- 239000002077 nanosphere Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000010406 cathode material Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OQBLGYCUQGDOOR-UHFFFAOYSA-L 1,3,2$l^{2}-dioxastannolane-4,5-dione Chemical compound O=C1O[Sn]OC1=O OQBLGYCUQGDOOR-UHFFFAOYSA-L 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- JRLDUDBQNVFTCA-UHFFFAOYSA-N antimony(3+);trinitrate Chemical compound [Sb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JRLDUDBQNVFTCA-UHFFFAOYSA-N 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000011246 composite particle Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- -1 stirring Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- BRCWHGIUHLWZBK-UHFFFAOYSA-K bismuth;trifluoride Chemical compound F[Bi](F)F BRCWHGIUHLWZBK-UHFFFAOYSA-K 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- YUOWTJMRMWQJDA-UHFFFAOYSA-J tin(iv) fluoride Chemical compound [F-].[F-].[F-].[F-].[Sn+4] YUOWTJMRMWQJDA-UHFFFAOYSA-J 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- H01M4/38—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
- H01M4/58—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
- H01M4/582—Halogenides
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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
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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
- 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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Abstract
The invention relates to the technical field of electrochemistry and batteries, in particular to a carbon-coated metal fluoride modified silicon anode material, a preparation method and application thereof, wherein the material is a Si/MFx@NC composite material, the innermost layer of the Si/MFx@NC composite material is nano silicon, the outermost layer is a carbon coating layer, and a metal fluoride is constructed between the carbon coating layer and the nano siliconA layer. The preparation method comprises the following steps: dissolving metal salt in glycol, and performing ultrasonic treatment for 30min to uniformly disperse the metal salt to obtain a homogeneous solution A; taking NH 4 F, adding the nano silicon powder into ethylene glycol, and stirring to dissolve and disperse the nano silicon powder uniformly to obtain a solution B; uniformly mixing the solution A and the solution B, stirring at normal temperature for reaction for 8-15h, filtering, washing, drying to obtain powder, dispersing the powder in Tris solution, adding a carbon source, and calcining under inert protective gas to obtain Si/MF x NC composite material. When the material is used as a battery cathode, the battery has the advantages of high stability, long cycle life, good multiplying power performance and the like.
Description
Technical Field
The invention relates to the technical field of electrochemistry and batteries, in particular to a carbon-coated metal fluoride modified silicon anode material and a preparation method and application thereof.
Background
The lithium ion battery has been widely used in portable electronic devices and hybrid vehicles due to its advantages of high energy density, long cycle life, environmental friendliness, and the like. In recent years, with the increasing demand for portable devices and the rapid development of hybrid vehicles, the energy density of lithium ion batteries is facing higher demands. As an important component of the lithium ion battery, the improvement of the electrochemical performance of the cathode material plays a great role in improving the overall energy density of the lithium ion battery. However, currently commercial graphite anode materials are only 372mAh g -1 This is not satisfactory for the pursuit of high energy density lithium ion batteries. Therefore, it is urgent to find a high-capacity anode material.
Silicon has an ultra-high theoretical capacity (4200 mAh g) -1 ) Is one of the most attractive negative electrode materials. Unfortunately, due to the problems associated with silicon anodes, including low electron conductivity, poor Li + Diffusion rate and huge volume expansion (400%) during lithiation/delithiation. Thus, silicon anodes generally exhibit poor electrochemical performance, including rate capability and cycling stabilityThe practical application of the silicon-based material in the lithium ion battery is greatly limited due to the property. Therefore, the development of the Si anode material with good cycle stability, long cycle life and good rate performance is an important subject, and has important significance for breaking through the application bottleneck of the material and accelerating the commercial application of the Si anode material.
Disclosure of Invention
The invention aims at: aiming at the problems, the carbon-coated metal fluoride modified silicon anode material, the preparation method and the application thereof are provided, and when the material is used as a battery anode, the battery has the advantages of high stability, long cycle life, good rate capability and the like.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: the carbon-coated metal fluoride modified silicon anode material is a Si/MFx@NC composite material, wherein the innermost layer of the Si/MFx@NC composite material is nano silicon, the outermost layer is a carbon coating layer, and a metal fluoride layer is constructed between the carbon coating layer and the nano silicon.
The preparation method of the carbon-coated metal fluoride modified silicon anode material comprises the following steps:
(1) Dissolving metal salt in glycol, and performing ultrasonic treatment for 30min to uniformly disperse the metal salt to obtain a homogeneous solution A; taking NH 4 F, adding the nano silicon powder into ethylene glycol, and stirring to dissolve and disperse the nano silicon powder uniformly to obtain a solution B;
(2) Uniformly mixing the solution A and the solution B, stirring at normal temperature for reaction for 8-15h, filtering, washing and drying to obtain powder, namely a Si/MFx precursor;
(3) Dispersing the Si/MFx precursor in a Tris solution, adding a carbon source, stirring, filtering, washing and drying to obtain black powder which is an Si/MFx@PDA intermediate product;
(4) Placing the Si/MFx@PDA intermediate product in a ceramic square boat, sealing a tubular furnace, introducing inert protective gas, calcining, and naturally cooling to room temperature to obtain the Si/MFx@NC composite material.
In the preparation method, in the step (1), the metal salt is one or more of nitrate, sulfate and oxalate of Sn, bi, sb, zn.
In the preparation method, in the step (1), the mass ratio of the silicon powder to the NH4F is 1:2The method comprises the steps of carrying out a first treatment on the surface of the The saidMetal salts and NH 4 F molar ratio is MF x The molar ratio of M to F elements in the formula is 1:x.
In the preparation method, in the step (3), the carbon source is one or more of dopamine hydrochloride, resorcinol polyacrylonitrile, glucose and citric acid.
In the preparation method, in the step (3), the dosage of the carbon source is 5-20% of the mass of the metal salt.
In the above preparation method, in the step (4), the inert shielding gas is pure nitrogen or pure argon
In the preparation method, in the step (4), the calcination temperature is 500-800 ℃, and the calcination time is 0.5-1h.
The invention also provides application of the carbon-coated metal fluoride modified silicon anode material in a lithium ion battery.
In summary, due to the adoption of the technical scheme, the invention has the following beneficial effects:
1. according to the invention, the surface of the silicon nanoparticle is modified by introducing the superfine metal fluoride with lithium storage activity, when lithium ions provided by the anode come to the cathode, conversion reaction and alloying reaction are carried out between the superfine metal fluoride and the metal fluoride, and the metal fluoride can be used for storing the lithium ions and providing high specific capacity, so that the lithium ions and the electron transmission rate are improved; and meanwhile, a gap designed by the carbon coating can provide buffer space for the volume expansion of silicon.
2. Si/MF of the present invention x The @ NC composite material can be used as a negative electrode material of a secondary lithium battery, and when the NC composite material is used as the negative electrode material of a lithium ion battery, the transmission path of ions can be shortened, the conductivity of the material can be improved, and the structural stability of the material can be improved, so that the prepared lithium ion battery has the advantages of high stability, long cycle life, good multiplying power performance and the like, and can effectively meet the actual application requirements of the high-performance lithium ion battery, and therefore, the material prepared by the invention is an ideal lithium ion battery negative electrode with great application prospectA polar material.
3. Si/MF prepared by the method x The @ NC nanosphere composite material is a lithium ion battery cathode material, and the prepared Si/MF x The size of the @ NC nanosphere composite material reaches tens to hundreds of nanometers, and the composite material has high purity, strong crystallinity and uniform morphology.
4. The one-step liquid reaction process used by the invention has the advantages of short reaction flow, simple process, low-cost and easily-obtained raw materials, high yield, uniform product structure and appearance, easy control and accordance with the requirements of large-scale industrial application.
Drawings
FIG. 1 is a Si/BiF 3 SEM image of NC composite.
FIG. 2 is a Si/BiF 3 TEM image of NC composite.
FIG. 3 is a Si/BiF 3 Charge-discharge curve plot for NC electrode.
FIG. 4 is a Si/BiF 3 At 0.5Ag for NC electrode -1 The following cycle performance graph.
FIG. 5 is a Si/BiF 3 NC electrode at 1.0Ag -1 The following cycle performance graph.
FIG. 6 is Si/SnF 2 SEM image of NC composite.
FIG. 7 is Si/SnF 2 TEM image of NC composite.
FIG. 8 is Si/SnF 2 Charge-discharge curve diagram of NC electrode
FIG. 9 is Si/SnF 2 At 0.2Ag for NC electrode -1 The following cycle performance graph.
FIG. 10 is a Si/SnF 2 NC electrode at 1.0Ag -1 The following cycle performance graph.
Detailed Description
The present invention will be further described with reference to the following examples in order to more clearly illustrate the present invention.
Example 1
(1) 232mg of bismuth nitrate is weighed and dissolved in glycol, and ultrasonic treatment is carried out for 30min, so that the bismuth nitrate is uniformly dispersed to obtain a solution A; the mass ratio of silicon powder to NH4F is 1:2 weighing NH 4 F and nano silicon powder are dissolved in glycol by stirringUniformly dispersing to obtain a solution B;
(2) Transferring the solution A and the solution B obtained in the step (1) into the same beaker, uniformly mixing by magnetic stirring, stirring and reacting for 8 hours at 25 ℃, filtering, washing and drying to obtain powder, namely Si/BiF 3 A precursor;
(3) Taking the Si/BiF obtained in the step (2) 3 Dispersing the precursor in Tris solution, adding dopamine hydrochloride, wherein the mass of the dopamine hydrochloride is 5% of that of bismuth nitrate in the step (1), stirring, filtering, washing and drying to obtain black powder which is Si/BiF 3 PDA intermediate;
(4) The Si/BiF obtained in the step (3) is processed 3 Placing the @ PDA intermediate product in a ceramic ark, sealing a tube furnace, introducing pure nitrogen, calcining at 500 ℃ for 1h, and naturally cooling to room temperature to obtain Si/BiF 3 @ NC composite material.
For the Si/BiF prepared in this example 3 SEM analysis of @ NC composite material, the SEM spectrum of which is shown in FIG. 1, and Si/BiF can be seen from FIG. 1 3 The @ NC composite particles are represented as nanoparticles, and the particle surface has small particles attached to the surface.
For the Si/BiF prepared in this example 3 TEM analysis was performed on the @ NC composite material, and the TEM spectrum thereof is shown in FIG. 2. From FIG. 2, it can be seen that Si/BiF 3 the@NC composite material can be used for seeing that small-particle nano bismuth fluoride is attached to the surface of large-particle nano silicon, and the morphology is consistent with that of a scanning electron microscope.
Example 2
(1) Weighing 232mg of stannous oxalate, dissolving in ethylene glycol, and carrying out ultrasonic treatment for 30min to uniformly disperse the stannous oxalate to obtain a solution A; weighing NH according to the mole ratio of Sn to F=1 to 2 and the mass ratio of silicon powder to NH4F of 1 to 2 4 F, adding the nano silicon powder into ethylene glycol, and stirring to dissolve and disperse the nano silicon powder uniformly to obtain a solution B;
(2) Transferring the solution A and the solution B obtained in the step (1) into the same beaker, uniformly mixing by magnetic stirring, stirring and reacting for 15 hours at 25 ℃, filtering, washing and drying to obtain powder, namely Si/SnF 2 A precursor;
(3) Taking the Si/SnF obtained in the step (2) 2 Dispersing the precursor in Tris solution, adding resorcinol polyacrylonitrile, wherein the mass of resorcinol polyacrylonitrile is 20% of that of stannous chloride in the step (1), stirring, filtering, washing and drying to obtain black powder which is Si/SnF 2 PDA intermediate;
(4) The Si/SnF obtained in the step (3) is processed 2 Placing the @ PDA intermediate product in a ceramic ark, sealing a tube furnace, introducing pure argon, calcining at 800 ℃ for 0.5h, and naturally cooling to room temperature to obtain Si/SnF 2 @ NC composite material.
For the Si/SnF prepared in this example 2 SEM analysis of @ NC composite material, the SEM spectrum of which is shown in FIG. 6, and Si/SnF can be seen from FIG. 6 2 The @ NC composite particles are represented by nanoparticles, and the surfaces of the particles have nanosheets attached to the surfaces.
For the Si/SnF prepared in this example 2 TEM analysis is carried out on the @ NC composite material, the TEM spectrum of the @ NC composite material is shown in FIG. 7, and the Si/SnF can be seen from FIG. 7 2 The @ NC composite material can be used for seeing that the tin fluoride nano-sheet is attached to the surface of the large-particle nano-silicon, and the appearance is consistent with that of a scanning electron microscope.
Example 3
(1) Weighing 195mg of antimony nitrate, dissolving in glycol, and carrying out ultrasonic treatment for 30min to uniformly disperse the antimony nitrate to obtain a solution A; weighing NH according to the mole ratio of Sb to F=1:3 and the mass ratio of silicon powder to NH4F of 1:2 4 F, adding the nano silicon powder into ethylene glycol, and stirring to dissolve and disperse the nano silicon powder uniformly to obtain a solution B;
(2) Transferring the solution A and the solution B obtained in the step (1) into the same beaker, uniformly mixing by magnetic stirring, stirring and reacting for 10 hours at 25 ℃, filtering, washing and drying to obtain powder, namely Si/SbF 3 A precursor;
(3) Taking the Si/SbF obtained in the step (2) 3 Dispersing the precursor in Tris solution, adding glucose with the mass of 15% of the mass of antimony chloride in the step (1), stirring, filtering, washing, and drying to obtain black powder which is Si/SbF 3 PDA intermediate;
(4) Will beSi/SbF obtained in step (3) 3 Placing the @ PDA intermediate product in a ceramic ark, sealing a tube furnace, introducing pure nitrogen, heating at 600 ℃ for 1h, and naturally cooling to room temperature to obtain Si/SbF 3 @ NC composite material.
Electrochemical performance test
The product materials prepared in examples 1 and 2 were respectively prepared into negative electrodes, and assembled into batteries, and the cycle performance of the batteries was tested by the following specific method: mixing the product material, conductive carbon black Super P, binder CMC and deionized water, stirring, coating the slurry on a current collector copper foil, drying at 60 ℃ to obtain a negative plate, taking a metal lithium plate as a positive electrode, polypropylene as a diaphragm and LiPF6 as electrolyte, and assembling in a glove box filled with argon to obtain the CR2025 button experiment battery.
The test shows that:
1)Si/BiF 3 when the @ NC nanosphere composite material is used as an anode material of an ion battery, a first charge-discharge curve of the battery is shown in figure 3, the first discharge specific capacity is 1939.2mAh/g, the charge specific capacity is 1385.1mAh/g, and the first coulomb efficiency is 140%; after 175 circles of the material is circulated at 25 ℃ with the current density of 500mA/g, the reversible specific capacity is 820mAh/g, and the circulation performance chart is shown in figure 4; after 450 circles of circulation at the current density of 1000mA/g, the reversible specific capacity is 955.8mAh/g, and the circulation performance chart is shown in FIG. 5; from the above test data, si/BiF 3 When the @ NC nanosphere composite material is used as a cathode material of an ion battery, the battery has high capacity and good stability, and shows excellent electrochemical performance.
2)Si/SnF 2 When the @ NC nanosphere composite material is used as a lithium ion battery cathode material, a first charge-discharge curve of the battery is shown in fig. 8, the first discharge specific capacity is 1997.4mAh/g, the charge specific capacity is 1602.5mAh/g, and the first coulomb efficiency is 124.6%; after 280 circles of circulation at 25 ℃ and a current density of 200mA/g, the reversible specific capacity is 1150mAh/g, and the circulation performance diagram is shown in FIG. 9; after 600 cycles of current density of 1000mA/g, the reversible specific capacity is 1039mAh/g, and the cycle performance chart is shown in FIG. 10. By the following methodThe above test data shows that Si/SnF 2 When the @ NC nanosphere composite material is used as a cathode material of an ion battery, the battery has high capacity and good stability, and shows excellent electrochemical performance.
As can be seen from the above, the Si/MF prepared by the present invention x When the NC composite material is used as a negative electrode material of a lithium ion battery, the NC composite material has the advantages of high stability, long cycle life, good multiplying power performance and the like, because the superfine metal fluoride with lithium storage activity is introduced to modify the surface of silicon nano particles, when lithium ions provided by a positive electrode come to a negative electrode, conversion reaction and alloying reaction are carried out between the superfine metal fluoride and the metal fluoride, the metal fluoride can be used for storing the lithium ions, and high specific capacity is provided, so that the transmission rate of the lithium ions and electrons is improved, the coulomb efficiency is improved, the transmission path of the ions is shortened, and the conductivity of the material is improved; meanwhile, a buffer space can be provided for the volume expansion of silicon in a gap of carbon cladding design, and the structural stability of the material is improved.
The foregoing description is directed to the preferred embodiments of the present invention, but the embodiments are not intended to limit the scope of the invention, and all equivalent changes or modifications made under the technical spirit of the present invention should be construed to fall within the scope of the present invention.
Claims (9)
1. The carbon-coated metal fluoride modified silicon anode material is characterized in that the material is a Si/MFx@NC composite material, the innermost layer of the Si/MFx@NC composite material is nano silicon, the outermost layer is a carbon coating layer, and a metal fluoride layer is constructed between the carbon coating layer and the nano silicon.
2. The method for preparing a carbon-coated metal fluoride-modified silicon negative electrode material according to claim 1, comprising the steps of:
(1) Dissolving metal salt in glycol, and performing ultrasonic treatment for 30min to uniformly disperse the metal salt to obtain a homogeneous solution A; taking NH 4 F, adding the nano silicon powder into ethylene glycol, and stirring to dissolve and disperse the nano silicon powder uniformly to obtain a solution B;
(2) Uniformly mixing the solution A and the solution B, stirring at normal temperature for reaction for 8-15h, filtering, washing and drying to obtain powder, namely a Si/MFx precursor;
(3) Dispersing the Si/MFx precursor in a Tris solution, adding a carbon source, stirring, filtering, washing and drying to obtain black powder which is an Si/MFx@PDA intermediate product;
(4) Placing the Si/MFx@PDA intermediate product in a ceramic square boat, sealing a tubular furnace, introducing inert protective gas, calcining, and naturally cooling to room temperature to obtain the Si/MFx@NC composite material.
3. The method according to claim 2, wherein in the step (1), the metal salt is one or more of nitrate, sulfate and oxalate of Sn, bi, sb, zn.
4. The method of claim 2, wherein in step (1), the mass ratio of the silicon powder to NH4F is 1:2The method comprises the steps of carrying out a first treatment on the surface of the The saidMetal salts and NH 4 F molar ratio is MF x The molar ratio of M to F elements in the formula is 1:x.
5. The method according to claim 2, wherein in the step (3), the carbon source is one or more of dopamine hydrochloride, resorcinol polyacrylonitrile, glucose and citric acid.
6. The method according to claim 2, wherein in the step (3), the carbon source is used in an amount of 5 to 20% by mass of the metal salt.
7. The method of claim 2, wherein in step (4), the inert shielding gas is pure nitrogen or pure argon.
8. The method according to claim 2, wherein in the step (4), the calcination is carried out at a temperature of 500 to 800 ℃ for a time of 0.5 to 1 hour.
9. Use of the carbon-coated metal fluoride modified silicon negative electrode material of claim 1 or the carbon-coated metal fluoride modified silicon negative electrode material prepared by the preparation method of any one of claims 2 to 8 in a lithium ion battery.
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