CN116443920B - Tin-based composite material and preparation method and application thereof - Google Patents
Tin-based composite material and preparation method and application thereof Download PDFInfo
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- CN116443920B CN116443920B CN202310443542.5A CN202310443542A CN116443920B CN 116443920 B CN116443920 B CN 116443920B CN 202310443542 A CN202310443542 A CN 202310443542A CN 116443920 B CN116443920 B CN 116443920B
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- 239000002131 composite material Substances 0.000 title claims abstract description 54
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 21
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims abstract description 18
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000012266 salt solution Substances 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 9
- 238000000227 grinding Methods 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 239000012298 atmosphere Substances 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 230000001681 protective effect Effects 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 15
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 13
- 229910052744 lithium Inorganic materials 0.000 description 13
- 239000000047 product Substances 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 238000001237 Raman spectrum Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000011366 tin-based material Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000006245 Carbon black Super-P Substances 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
- 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
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 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
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000002733 tin-carbon composite material Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
- C01G19/02—Oxides
-
- 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
- H01M4/48—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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a tin-based composite material, a preparation method and application thereof. The preparation method of the tin-based composite material comprises the following steps: (1) Preparing a soluble tin salt solution and an EDTA solution, adding the EDTA solution into the soluble tin salt solution, continuously stirring for reaction, filtering after the reaction is finished to obtain a product, and washing and drying the product to obtain a Sn-EDTA precursor; (2) And (3) calcining the Sn-EDTA precursor in the step (1) in a protective gas atmosphere, and grinding after calcining to obtain the tin-based composite material. The tin-based composite material prepared by the invention is used for preparing a lithium ion battery cathode, and is assembled into a lithium ion battery, and has excellent rate reversibility and relatively stable coulombic efficiency.
Description
Technical Field
The invention belongs to the technical field of energy storage materials, and particularly relates to a tin-based composite material, and a preparation method and application thereof.
Background
The lithium ion battery has the advantages of higher energy density, environmental friendliness, no memory effect and the like, and is widely applied to living scenes. With the continuous progress of society, higher requirements are placed on the performance of lithium ion batteries, such as higher safety performance, longer cycle life, and better rate capability. At present, the theoretical specific capacity of a commercial graphite negative electrode is smaller (372 mAh g -1), and the low lithium intercalation potential is easy to cause the phenomenon of lithium precipitation in the high-rate charging process. Therefore, the development of a non-carbon negative electrode material with excellent performance is a hot spot in the development of lithium ion batteries. Tin-based materials are considered to be the most promising negative electrode materials for lithium ion batteries because of their high specific capacity (700-1400 mAh g -1) and suitable charge-discharge potential (-0.6V vs Li +/Li). However, the volume of the tin-based material is greatly expanded and contracted in the lithium intercalation process, deformation, crushing and pulverization are generated, and the electrical performance is reduced.
At present, the electrochemical performance of tin-based materials is improved mainly by carbon coating. The preparation process generally requires synthesis of tin oxide first, followed by hydrothermal coating of amorphous carbon or expensive graphene, and finally pyrolytic carbonization, etc. to obtain carbon coated products. The process is complex, the steps are complicated, and the further application of the method is limited. Therefore, a tin-based composite material preparation process with simple flow and low cost needs to be developed.
Disclosure of Invention
Aiming at overcoming the defects of the prior art, the invention aims to provide a tin-based composite material and a preparation method and application thereof. The tin-based composite material with excellent lithium storage performance is prepared by the method, the volume expansion and particle crushing of the tin-based material in the charge and discharge process are effectively relieved, and the cycle life of the battery is prolonged.
The aim of the invention is achieved by the following technical scheme:
the preparation method of the tin-based composite material comprises the following steps:
(1) Preparing a soluble tin salt solution and an EDTA solution, wherein the molar ratio of tin in the soluble tin salt solution to EDTA in the EDTA solution is 1:0.5 to 3; then adding EDTA solution into the soluble tin salt solution, continuously stirring for reaction, filtering after the reaction is finished to obtain a product, and washing and drying the product to obtain a Sn-EDTA precursor;
(2) And (3) calcining the Sn-EDTA precursor in the step (1) in a protective gas atmosphere, and grinding after calcining to obtain the tin-based composite material.
Preferably, in step (1), the molar concentration ratio of the soluble tin salt solution to the EDTA solution is 1:1 to 3.
Preferably, in step (1), the reaction time is 2 to 24 hours, more preferably 10 hours.
Preferably, in step (1), the washing mode is as follows: washing with water followed by ethanol.
Preferably, in step (1), the tin salt in the soluble tin salt solution is at least one of SnCl 4、SnCl2 and SnSO 4.
Preferably, in the step (1), the drying temperature is 60-100 ℃, and the drying time is 5-24 hours.
Preferably, in the step (1), the solvent of the soluble tin salt solution is at least one of water, ethanol, ethylene glycol and glycerol.
Preferably, in step (1), the solvent of the EDTA solution is water.
Preferably, in the step (2), the shielding gas is argon or nitrogen.
Preferably, in the step (2), the calcination temperature is 500-800 ℃ and the calcination time is 2-10 h. The final product will vary with the calcination temperature.
The tin-based composite material prepared by the preparation method of the tin-based composite material.
The tin-based composite material is applied to preparation of a lithium ion battery anode material.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, through the complexation reaction, the tin atoms in the precursor are uniformly distributed, the tin agglomeration phenomenon in the calcination process can be effectively controlled, the tin-based compound is uniformly encapsulated in the carbon layer, and the volume change of the tin-based negative electrode in the charge and discharge process is effectively relieved.
2. According to the invention, a series of tin-based composite materials SnO x -C (x is more than or equal to 0 and less than or equal to 2) with different structures can be prepared through the regulation and control of the calcination temperature.
3. The preparation process is simple, environment-friendly and easy to scale.
Drawings
FIG. 1 is an XRD pattern of SnO x -C composite material and SnO standard card prepared in example 1.
FIG. 2 is a Raman spectrum of the SnO x -C composite material prepared in example 1.
Fig. 3 is a graph showing the first and second charge and discharge performance of the SnO x -C composite assembled lithium ion battery with high lithium storage performance prepared in example 1 at a current density of 200 mg -1.
FIG. 4 is a graph showing the cycling performance of the SnO x -C composite material with high lithium storage performance prepared in example 1 at a current density of 200mAg -1.
Fig. 5 shows the cycling performance of SnO x -C composites with high lithium storage properties prepared in example 1 at different current densities.
FIG. 6 is an XRD pattern of SnO x -C composite material and Sn standard card prepared in example 3.
FIG. 7 is a Raman spectrum of SnO x -C composite material prepared in example 3.
Fig. 8 is a graph of the first and second charge and discharge performance of the SnO x -C composite assembled lithium ion battery with high lithium storage performance prepared in example 3 at 200 mg -1 current density.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. 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.
Example 1
The preparation method of the tin-based composite material comprises the following steps:
5mmol of SnCl 4 is dissolved in 50ml of water to prepare solution A; 5mmol of EDTA was dissolved in 50ml of water to prepare a solution B. Slowly adding the solution B into the solution A at room temperature, continuously stirring for 10 hours, centrifuging the product, washing the product with water and ethanol sequentially, and then drying the product in a blowing drying oven at 80 ℃ to obtain a Sn-EDTA precursor; and (3) putting the Sn-EDTA precursor into a tube furnace, introducing inert gas Ar, then raising the temperature to 600 ℃ at a heating rate of 2 ℃/min, keeping the temperature for 2 hours, cooling to room temperature, and grinding the product (grinding by an agate mortar for 30 minutes) to obtain the tin-based composite material, namely the SnO x -C composite material.
Example 2
The SnO x -C composite material prepared in example 1 is used for preparing a lithium ion battery anode material.
The preparation method of the lithium ion battery comprises the following steps: uniformly mixing the SnO x -C composite material prepared in the example 1, a conductive agent (Super-P) and a binder (sodium carboxymethylcellulose) in water according to the mass ratio of 70:15:15, coating the mixture on a copper foil to prepare an electrode slice, and carrying out vacuum drying; in an argon atmosphere glove box, with metallic lithium as a counter electrode, 1M LiPF 6 was dissolved in ec+dec+emc (1:1:1v%) +10% FEC as electrolyte, assembled into 2025 coin cells for testing. The test conditions were: the charge-discharge current density is 0.2-10A/g, and the charge-discharge cut-off voltage is 0.01-2.0V.
FIG. 1 is an XRD pattern of the SnO x -C composite material prepared in example 1. The composite material prepared in example 1 is known to be a SnO-C composite material by comparison with the SnO standard card PDF: 85-0712. FIG. 2 is a Raman spectrum of the SnO x -C composite material prepared in example 1, in which the presence of D and G peaks of carbon can be clearly observed, indicating that the material prepared in example 1 contains carbon.
Fig. 3 is a graph of the first and second charge and discharge performance of the SnO x -C composite assembled lithium ion battery with high lithium storage performance prepared in example 1 at a current density of 200 mg -1, and it can be observed that the specific capacities of the composite for the first and second discharge are 1526.8 and 996.4mAh g -1, respectively.
FIG. 4 is a graph showing the cycling performance of the SnO x -C composite material with high lithium storage performance prepared in example 1 at a current density of 200mAg -1, wherein the reversible capacity of 574mAh g -1 after 200 cycles can be observed; and the coulomb efficiency is relatively stable in the whole circulation process, which is about 97.9 percent.
FIG. 5 shows the cycling performance of the SnO x -C composite material with high lithium storage performance prepared in example 1 at different current densities, and the reversible capacity of the composite material at 2A g -1 current density can be observed to be 320mAh g -1; and the coulomb efficiency is relatively stable in the circulation process under different current densities, and is about 97.7%, which indicates that the material has excellent rate reversibility.
Example 3
The preparation method of the tin-based composite material comprises the following steps:
5mmol of SnCl 4 is dissolved in 50ml of water to prepare solution A; 5mmol of EDTA was dissolved in 50ml of water to prepare a solution B. Slowly adding the solution B into the solution A at room temperature, continuously stirring for 10 hours, centrifuging the product, washing the product with water and ethanol sequentially, and then drying the product in a blowing drying oven at 80 ℃ to obtain a Sn-EDTA precursor; and (3) putting the Sn-EDTA precursor into a tube furnace, introducing inert gas Ar, then raising the temperature to 700 ℃ at a heating rate of 2 ℃/min, keeping the temperature for 2 hours, cooling to room temperature, and grinding the product (grinding by an agate mortar for 30 minutes) to obtain the tin-based composite material, namely the SnO x -C composite material.
Example 4
The SnO x -C composite material prepared in example 3 is used for preparing a lithium ion battery cathode material, and a lithium ion battery is prepared and tested in the same method as in example 1.
FIG. 6 is an XRD pattern of SnO x -C composite material prepared in example 3. As can be seen from comparison with the Sn standard card PDF 86-2265, the material prepared in example 1 is a Sn-C composite material.
FIG. 7 is a Raman spectrum of the SnO x -C composite material prepared in example 3, in which the presence of D and G peaks of carbon can be clearly observed, indicating that the material prepared in example 3 contains carbon.
Fig. 8 is a graph of the first and second charge/discharge performance of the SnO x -C composite assembled lithium ion battery with high lithium storage performance prepared in example 3 at a current density of 200 mg -1, and it can be observed that the specific capacities of the composite for the first and second discharge are 1280.9mAh g -1 and 896.8mAh g -1, and the initial efficiency is 63.5%.
The above-described embodiments of the present invention do not limit the scope of the present invention. Any other corresponding changes and modifications made in accordance with the technical idea of the present invention shall be included in the scope of the claims of the present invention.
Claims (7)
1. The preparation method of the tin-based composite material is characterized by comprising the following steps:
(1) Preparing a soluble tin salt solution and an EDTA solution, wherein the molar ratio of tin in the soluble tin salt solution to EDTA in the EDTA solution is 1: 0.5-3; then adding EDTA solution into the soluble tin salt solution, continuously stirring for reaction, filtering after the reaction is finished to obtain a product, and washing and drying the product to obtain a Sn-EDTA precursor;
the solvent of the soluble tin salt solution in the step (1) is at least one of water, ethanol, glycol and glycerol;
The solvent of the EDTA solution in the step (1) is water;
(2) Calcining the Sn-EDTA precursor in the step (1) in a protective gas atmosphere, and grinding after calcining to obtain the tin-based composite material;
The chemical structural formula of the tin-based composite material is SnO x -C, wherein x is more than or equal to 0 and less than or equal to 2;
And (2) calcining at 500-800 ℃ for 2-10 hours.
2. The method for preparing a tin-based composite material according to claim 1, wherein the molar concentration ratio of the soluble tin salt solution to the EDTA solution in the step (1) is 1: 1-3.
3. The method for preparing a tin-based composite material according to claim 2, wherein the drying temperature in the step (1) is 60-100 ℃ and the drying time is 5-24 hours.
4. The method for preparing a tin-based composite material according to any one of claims 1 to 3, wherein the reaction time in the step (1) is 2 to 24 hours.
5. The method for preparing a tin-based composite material according to any one of claims 1 to 3, wherein the tin salt in the soluble tin salt solution in the step (1) is at least one of SnCl 4、SnCl2 and SnSO 4.
6. The method for preparing a tin-based composite material according to claim 5, wherein the washing in the step (1) is performed by: washing with water followed by ethanol.
7. The method of claim 6, wherein the shielding gas in step (2) is argon or nitrogen.
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| CN102208605A (en) * | 2011-04-25 | 2011-10-05 | 长安大学 | Method for preparing tin-carbon nano composite electrode material |
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| CN102208605A (en) * | 2011-04-25 | 2011-10-05 | 长安大学 | Method for preparing tin-carbon nano composite electrode material |
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