CN112490414A - Tin dioxide and vanadium pentoxide composite electrode material and preparation method and application thereof - Google Patents
Tin dioxide and vanadium pentoxide composite electrode material and preparation method and application thereof Download PDFInfo
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- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 title claims abstract description 142
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title claims abstract description 129
- 239000002131 composite material Substances 0.000 title claims abstract description 45
- 239000007772 electrode material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000008367 deionised water Substances 0.000 claims description 26
- 229910021641 deionized water Inorganic materials 0.000 claims description 26
- -1 sodium stannate tetrahydrate Chemical class 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 7
- 238000004108 freeze drying Methods 0.000 claims description 7
- 239000000017 hydrogel Substances 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000003760 magnetic stirring Methods 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 229940079864 sodium stannate Drugs 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 229910013872 LiPF Inorganic materials 0.000 claims description 4
- 101150058243 Lipf gene Proteins 0.000 claims description 4
- 239000010406 cathode material Substances 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 239000011889 copper foil Substances 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 2
- 239000011149 active material Substances 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000004146 energy storage Methods 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 239000000843 powder Substances 0.000 abstract description 2
- 230000001351 cycling effect Effects 0.000 abstract 1
- 238000005265 energy consumption Methods 0.000 abstract 1
- 230000008014 freezing Effects 0.000 abstract 1
- 238000007710 freezing Methods 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 239000010405 anode material Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 239000002077 nanosphere Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 239000002127 nanobelt Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002074 nanoribbon Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- 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
- H01M4/387—Tin or alloys based on tin
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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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- Engineering & Computer Science (AREA)
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- Composite Materials (AREA)
- Materials Engineering (AREA)
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a stannic oxide and vanadium pentoxide composite electrode material (SnO)2‑V2O5) Belonging to the technical field of functional nano materials. Hydrothermally preparing stannic oxide (SnO)2) Powder and vanadium pentoxide (V)2O5) And adding water into the gel, mixing, stirring, freezing and drying to obtain the tin dioxide and vanadium pentoxide composite electrode material. The stannic oxide and vanadium pentoxide composite electrode material prepared by the method has the characteristics of smaller electrochemical impedance, rapid ion transmission channel and the like, and shows excellent cycling stability and good times when being applied to energy storage of lithium ion batteriesHigh rate performance and high specific capacity. The whole electrode material is simple in preparation process, low in energy consumption, green and environment-friendly, and suitable for large-scale production.
Description
Technical Field
The invention relates to a design and preparation method of a tin dioxide and vanadium pentoxide composite electrode, and a negative electrode of a lithium ion battery prepared from the tin dioxide and vanadium pentoxide composite electrode, and belongs to the technical field of functional nano materials.
Background
Social development promotes the continuous increase of energy demand, leads to the annual increase of the consumption of non-renewable fossil energy, and causes serious ecological problems of global climate warming, atmospheric pollution and the like. Therefore, the development of clean energy which is environmentally friendly and can be continuously utilized is urgent. However, these energy sources are not uniformly distributed in time and space, and it is difficult to efficiently use them. In order to improve the utilization efficiency of energy, supercapacitors and secondary batteries have been produced. Among them, Lithium Ion Batteries (LIBs) have received much attention in the past decades due to their light weight, high energy density, stable cycle performance, and the like. The LIB, as an electrochemical energy storage and conversion system with advantages at present, has a wide application range, including hybrid vehicles, pure electric vehicles, solar and wind power generation energy storage, power station energy storage, electric tools, intelligent networks, and the like. The LIB is mainly composed of an anode, a cathode, a diaphragm, electrolyte and the like, and the performance of anode and cathode materials directly influences various performance indexes of the lithium ion battery. To date, many advances have been made in positive electrode materials, including currently marketed products such as lithium cobaltate, lithium manganate, lithium iron phosphate, and ternary materials. Relatively, the research and development of the negative electrode material are slightly insufficient, the industrialization variety is single, and the requirement of the high-performance power battery is difficult to meet.
Vanadium pentoxide has a high specific capacity and a relatively low cost as the negative electrode of LIB. If from V5+Is completely reduced to V0Its theoretical capacity is up to 1472mAh g-1Therefore, the material can be used as an electrode material for a high-performance negative electrode. Tin dioxide is due to its abundance and high theoretical capacity (782mAh g)-1) Is another anode material which is widely researched. However, in the practical application of tin dioxide, its large volume expansion leads to pulverization of the electrode material and rapid capacity fading.
One of the mitigation strategies is to build up heterostructures of tin dioxide with other materials in an attempt to account for excessive volume changes. Therefore, the development of two-dimensional tin dioxide and vanadium pentoxide composite electrode materials (nanobelts or nanosheets) may become an alternative method for effectively improving lithium storage performance. Wherein the nanoribbons can be cross-stackedStacked to form a densely packed network with a large number of adjacent interstitial spaces that can be interconnected to build up multiple vias. Furthermore, the network structure provides high conductivity for electron transport, in such a way that electron flow is greatly facilitated. There is already literature (SnO)2 Nanoparticles Anchored on 2D V2O5Nanosheets with enhanced lithium-Storage performance) prepares the stannic oxide and vanadium pentoxide composite electrode by a hydrothermal method, but the preparation process is complicated and the battery capacity is not high. Therefore, the tin dioxide and vanadium pentoxide composite electrode is prepared by a physical mixing and stirring method.
Disclosure of Invention
The invention aims to provide a preparation method of a tin dioxide and vanadium pentoxide composite electrode material, which is simple in preparation method and can realize high capacity and good cycle performance, aiming at the defects of a tin dioxide-based negative electrode material in the existing lithium ion battery.
The technical problem solved by the invention is as follows: a preparation method of a stannic oxide and vanadium pentoxide composite electrode material is provided, and the preparation method comprises the following steps: taking a proper amount of tin dioxide prepared by hydrothermal method, adding vanadium pentoxide with a mass less than that of the tin dioxide, finally adding a certain amount of deionized water, mixing and stirring, and freeze-drying to obtain the tin dioxide and vanadium pentoxide composite electrode material.
Preferably, the preparation method of the tin dioxide comprises the following steps: 0.1g of sodium stannate tetrahydrate and 0.24g of urea are charged into a beaker, then 25mL of deionized water and 15mL of ethanol are added under magnetic stirring and stirred until complete dissolution, and then the solution is transferred to a 100mL stainless steel reaction kettle lined with polytetrafluoroethylene and heated in an oven at 150 ℃ for 15 hours for hydrothermal reaction, after cooling to room temperature, the precipitate is separated by centrifugation, washed with deionized water and dried in a vacuum drying oven overnight for later use.
Preferably, the preparation method of the vanadium pentoxide comprises the following steps: and (3) filling 0.364g of vanadium pentoxide into a beaker, adding 15mL of deionized water and 5mL of hydrogen peroxide, reacting for 2h at room temperature, and stirring and heating the clear solution in an oil bath at 50 ℃ overnight to obtain the vanadium pentoxide hydrogel.
Preferably, the amount of deionized water used is less than the amount of vanadium pentoxide.
Preferably, the stirring time used is ≥ 1 h.
Preferably, the freeze-drying time used is greater than or equal to 12 h.
In order to solve the technical problems, the technical scheme provided by the invention is as follows: the electrode material is prepared by the tin dioxide and vanadium pentoxide composite electrode material.
In order to solve the technical problems, the technical scheme provided by the invention is as follows: the tin dioxide and vanadium pentoxide composite electrode material can be efficiently applied to a lithium ion battery cathode material.
Preferably, the preparation method of the material used as the lithium ion battery negative electrode material comprises the following steps:
a. drying the tin oxide and vanadium pentoxide composite electrode material coated on the copper foil in a vacuum drying oven at 60 ℃ for more than or equal to 24 hours, wherein the mass of the active material is about 0.8 mg;
b. lithium hexafluorophosphate LiPF (lithium hexafluorophosphate) 1.0M is contained in a mixed solution of ethylene carbonate EC, dimethyl carbonate DMC and methyl ethyl carbonate EMC (electro magnetic compatibility) with the volume ratio of 1:1:1 by taking a metal lithium sheet as a positive electrode6Is an electrolyte (1.0M LiPF)6/EC + DMC + EMC), button cells were assembled in a glove box with a polypropylene film as separator.
Preferably, all prepared electrodes have the current magnitude of 0.5A g when being used as lithium ion batteries for testing-1。
Has the advantages that:
compared with other methods for preparing the tin dioxide and vanadium pentoxide composite electrode material, the method for preparing the electrode material is simple, and is suitable for industrial large-scale production, which cannot be achieved by the previous method. The capacity of the prepared composite electrode is also the highest value in all reports at present. No harmful substances are generated in the preparation reaction process, and the preparation method conforms to the concept of green chemistry.
Adding less mass than tin dioxideBecause of its high theoretical capacity (1472mAh g)-1) And tin dioxide as the negative electrode of the lithium battery is very unstable, and the capacity is quickly attenuated. The present invention contemplates the use of a minimum of vanadium pentoxide to maintain the stability of the tin dioxide material as a negative electrode in a lithium battery. The amount of deionized water used is appropriate, and a proper amount of water can uniformly disperse a mixed system of vanadium pentoxide gel and tin dioxide powder, but excessive free water can reduce the voltage window, so that the battery performance is poor.
Drawings
The invention will be further explained with reference to the drawings.
FIG. 1 is a transmission electron microscope image of a composite electrode of tin dioxide and vanadium pentoxide in example 1 of the present invention;
FIG. 2 is an X-ray diffraction image of a tin dioxide and vanadium pentoxide composite electrode in example 1 of the present invention;
fig. 3 is a performance diagram of a lithium ion battery with a tin dioxide and vanadium pentoxide composite electrode in embodiment 1 of the present invention;
FIG. 4 is a plot of lithium ion battery performance for a directly prepared tin dioxide electrode in example 4 of the present invention;
FIG. 5 is a diagram of the preparation of the composite electrode material of tin dioxide and vanadium pentoxide.
Detailed Description
The technical solution of the invention is further illustrated below with reference to examples, which are not to be construed as limiting the technical solution.
Preparation of hollow structure stannic oxide nanosphere
The tin dioxide nanosphere with the hollow structure is synthesized by a hydrothermal method. In the experiment, 0.1g of sodium stannate tetrahydrate and 0.24g of urea were charged into a beaker, then 25mL of deionized water and 15mL of ethanol were added under magnetic stirring and stirred until completely dissolved, and then the above solution was transferred to a 100mL stainless steel reaction vessel lined with polytetrafluoroethylene and heated in an oven at 150 ℃ for 15 hours for hydrothermal reaction, after cooling to room temperature, the precipitate was separated by centrifugation, washed with deionized water, and dried in a vacuum drying oven overnight for use.
Preparation of vanadium di-pentoxide hydrogel
0.364g of vanadium pentoxide was charged into a beaker, and then 15mL of deionized water and 5mL of hydrogen peroxide were added and allowed to react at room temperature for 2 hours. Subsequently, the clear solution was heated in a 50 ℃ oil bath overnight with stirring to give a vanadium pentoxide hydrogel.
Preparation of composite electrode of tin dioxide and vanadium pentoxide
And (3) putting a proper amount of tin dioxide into a glass bottle, adding a certain amount of vanadium pentoxide and deionized water, mixing and stirring, and then carrying out freeze drying to obtain the tin dioxide and vanadium pentoxide composite electrode material.
Example 1
0.1g of sodium stannate tetrahydrate and 0.24g of urea are charged into a beaker, then 25mL of deionized water and 15mL of ethanol are added under magnetic stirring and stirred until complete dissolution, and then the solution is transferred to a 100mL stainless steel reaction kettle lined with polytetrafluoroethylene and heated in an oven at 150 ℃ for 15 hours for hydrothermal reaction, after cooling to room temperature, the precipitate is separated by centrifugation, washed with deionized water and dried in a vacuum drying oven overnight for later use.
0.364g of vanadium pentoxide was charged into a beaker, and then 15mL of deionized water and 5mL of hydrogen peroxide were added and allowed to react at room temperature for 2 hours. Subsequently, the clear solution was heated in an oven at 50 ℃ overnight to give a vanadium pentoxide hydrogel.
And (3) filling 35mg of tin dioxide into a glass bottle, then adding 2.5mL of vanadium pentoxide and 2mL of deionized water, mixing and stirring, and then carrying out freeze drying to obtain the tin dioxide and vanadium pentoxide composite electrode material.
The prepared stannic oxide and vanadium pentoxide composite electrode is 0.5A g-1After 300 cycles, the capacity is 683mAh g-1。
Example 2
0.1g of sodium stannate tetrahydrate and 0.24g of urea are charged into a beaker, then 25mL of deionized water and 15mL of ethanol are added under magnetic stirring and stirred until complete dissolution, and then the solution is transferred to a 100mL stainless steel reaction kettle lined with polytetrafluoroethylene and heated in an oven at 150 ℃ for 15 hours for hydrothermal reaction, after cooling to room temperature, the precipitate is separated by centrifugation, washed with deionized water and dried in a vacuum drying oven overnight for later use.
0.364g of vanadium pentoxide was charged into a beaker, and then 15mL of deionized water and 5mL of hydrogen peroxide were added and allowed to react at room temperature for 2 hours. Subsequently, the clear solution was heated in an oven at 50 ℃ overnight to give a vanadium pentoxide hydrogel.
And (3) filling 35mg of tin dioxide into a glass bottle, then adding 0.5mL of vanadium pentoxide and 2mL of deionized water, mixing and stirring, and then carrying out freeze drying to obtain the tin dioxide and vanadium pentoxide composite electrode material.
The prepared stannic oxide and vanadium pentoxide composite electrode is 0.5A g-1After 300 cycles, the capacity is 501mAh g-1。
Example 3
The composite electrode material of the tin dioxide and the vanadium pentoxide prepared by the invention can be directly used as a negative electrode of a lithium ion battery. And drying the electrode coated with the material on the copper foil in a vacuum drying oven at 60 ℃ for 24 hours. Using a lithium metal sheet as a positive electrode, 1.0M LiPF6And (3) taking a + EC/DMC/EMC (volume ratio of 1:1:1) solution as an electrolyte, taking a polypropylene film as a diaphragm, and assembling the button cell in a glove box to obtain the lithium ion battery, wherein the battery case is 2032.
After the battery assembly is completed and the battery is placed aside, a constant current charge-discharge cycle test is carried out on a battery tester (Shenzhen New Wei battery test cabinet CT-4008-5V5 mA), and the working voltage is 0.01-3V. After data acquisition was complete, mapping and analysis was performed by Origin data processing software.
Example 4
0.1g of sodium stannate tetrahydrate and 0.24g of urea are charged into a beaker, then 25mL of deionized water and 15mL of ethanol are added under magnetic stirring and stirred until complete dissolution, and then the solution is transferred to a 100mL stainless steel reaction kettle lined with polytetrafluoroethylene and heated in an oven at 150 ℃ for 15 hours for hydrothermal reaction, after cooling to room temperature, the precipitate is separated by centrifugation, washed with deionized water and dried in a vacuum drying oven overnight for later use.
The dried hollow tin dioxide was subjected to lithium ion battery testing under the test conditions as in example 2.
The prepared stannic oxide is 0.5A g-1After 300 cycles, the capacity is 239mAh g-1。
Example 5
0.364g of vanadium pentoxide was charged into a beaker, and then 15mL of deionized water and 5mL of hydrogen peroxide were added and allowed to react at room temperature for 2 hours. Subsequently, the clear solution was heated in an oven at 50 ℃ overnight to give a vanadium pentoxide hydrogel. Drying in a freeze dryer for later use.
And (3) testing the dried vanadium pentoxide on a lithium ion battery under the test conditions according to the example 2.
The prepared vanadium pentoxide is 0.2A g-1After circulating for 100 circles, the capacity is 623mAh g-1。
Example 6
The tin dioxide and vanadium pentoxide composite electrode prepared by the method is 0.5Ag-1After 300 cycles, the capacity is 683mAh g-1. At 0.2A g-1After circulating for 100 circles, the capacity is 839mAh g-1The electrode is the highest value of the currently reported tin dioxide and vanadium pentoxide composite electrode. The tin dioxide and vanadium pentoxide composite electrode is prepared in the prior literature, but the preparation process is complicated, is not suitable for large-scale production, and is 0.1A g-1After 200 cycles, the capacity is 721mAh g-1And the performance of the composite electrode prepared by the method is 0.5A g-1After 200 cycles, the capacity is 703mAh g-1. Although the capacity is not greatly different, the prepared electrode material can bear larger current and has better stability.
The invention is not limited to the specific technical solutions described in the above embodiments, and all technical solutions formed by equivalent substitutions are within the scope of the invention as claimed.
Claims (10)
1. A preparation method of a stannic oxide and vanadium pentoxide composite electrode material is characterized by comprising the following steps: the preparation method comprises the following steps: taking a proper amount of tin dioxide prepared by hydrothermal method, adding vanadium pentoxide with a mass less than that of the tin dioxide, finally adding a certain amount of deionized water, mixing and stirring, and freeze-drying to obtain the tin dioxide and vanadium pentoxide composite electrode material.
2. The preparation method of the tin dioxide and vanadium pentoxide composite electrode material as claimed in claim 1, wherein: the preparation method of the tin dioxide comprises the following steps: 0.1g of sodium stannate tetrahydrate and 0.24g of urea were charged into a beaker, then 25mL of deionized water and 15mL of ethanol were added with magnetic stirring and stirred until completely dissolved. Subsequently, the above solution was transferred to a 100mL stainless steel reaction vessel lined with polytetrafluoroethylene and heated in an oven at 150 ℃ for 15 hours for hydrothermal reaction, after cooling to room temperature, the precipitate was separated by centrifugation, washed with deionized water and dried in a vacuum oven overnight for further use.
3. The preparation method of the tin dioxide and vanadium pentoxide composite electrode material as claimed in claim 1, wherein: the preparation method of the vanadium pentoxide comprises the following steps: 0.364g of vanadium pentoxide was charged into a beaker, and then 15mL of deionized water and 5mL of hydrogen peroxide were added and allowed to react at room temperature for 2 hours. Subsequently, the clear solution was heated in a 50 ℃ oil bath overnight with stirring to give a vanadium pentoxide hydrogel.
4. The method for preparing the tin dioxide and vanadium pentoxide composite electrode material according to claim 1, wherein: the amount of deionized water used is less than the amount of vanadium pentoxide.
5. The method for preparing the tin dioxide and vanadium pentoxide composite electrode material according to claim 1, wherein: the required stirring time is more than or equal to 1 h.
6. The method for preparing the tin dioxide and vanadium pentoxide composite electrode material according to claim 1, wherein: the required freeze drying time is more than or equal to 12 hours.
7. The electrode material prepared from the tin dioxide and vanadium pentoxide composite electrode material according to claim 1.
8. The use of a tin dioxide and vanadium pentoxide composite electrode material according to claim 7, characterized in that: can be efficiently applied to the lithium ion battery cathode material.
9. The use of a tin dioxide and vanadium pentoxide composite electrode material according to claim 7, characterized in that: the preparation method of the material used as the lithium ion battery cathode material comprises the following steps:
a. drying the tin dioxide and vanadium pentoxide composite electrode material coated on the copper foil in a vacuum drying oven at 60 ℃ for more than or equal to 24 hours, wherein the mass of the active material is about 0.8 mg;
b. lithium hexafluorophosphate LiPF (lithium hexafluorophosphate) 1.0M is contained in a mixed solution of ethylene carbonate EC, dimethyl carbonate DMC and methyl ethyl carbonate EMC (electro magnetic compatibility) with the volume ratio of 1:1:1 by taking a metal lithium sheet as a positive electrode6Is an electrolyte (1.0M LiPF)6/EC + DMC + EMC), button cells were assembled in a glove box with a polypropylene film as separator.
10. The use of a tin dioxide and vanadium pentoxide composite electrode material according to claim 9, characterized in that: all prepared electrodes have the current magnitude of 0.5A g when being used as lithium ion batteries for testing-1Or 0.2A g-1。
Priority Applications (1)
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CN113555542A (en) * | 2021-09-18 | 2021-10-26 | 河南电池研究院有限公司 | Lithium ion battery cathode material and preparation method thereof |
CN114335482A (en) * | 2021-12-28 | 2022-04-12 | 陕西科技大学 | MnO (MnO)2-metal heterojunction composite material and preparation method and application thereof |
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CN106340633A (en) * | 2016-11-24 | 2017-01-18 | 杭州启澄科技有限公司 | Composite nano material for high performance lithium ion battery and preparation method thereof |
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CN114335482A (en) * | 2021-12-28 | 2022-04-12 | 陕西科技大学 | MnO (MnO)2-metal heterojunction composite material and preparation method and application thereof |
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