CN111900389B - Fe2VO4Ordered mesoporous carbon composite material and application thereof - Google Patents
Fe2VO4Ordered mesoporous carbon composite material and application thereof Download PDFInfo
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- CN111900389B CN111900389B CN202010457758.3A CN202010457758A CN111900389B CN 111900389 B CN111900389 B CN 111900389B CN 202010457758 A CN202010457758 A CN 202010457758A CN 111900389 B CN111900389 B CN 111900389B
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- 239000002131 composite material Substances 0.000 title claims abstract description 56
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 55
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 94
- 229910052742 iron Inorganic materials 0.000 claims description 28
- 229910052720 vanadium Inorganic materials 0.000 claims description 27
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 27
- 239000006185 dispersion Substances 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000012265 solid product Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- FSJSYDFBTIVUFD-SUKNRPLKSA-N (z)-4-hydroxypent-3-en-2-one;oxovanadium Chemical group [V]=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FSJSYDFBTIVUFD-SUKNRPLKSA-N 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 3
- 239000012300 argon atmosphere Substances 0.000 claims description 3
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims 1
- 239000012299 nitrogen atmosphere Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 13
- 239000010406 cathode material Substances 0.000 abstract description 6
- 238000005054 agglomeration Methods 0.000 abstract description 4
- 239000007773 negative electrode material Substances 0.000 abstract description 4
- 239000003792 electrolyte Substances 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000002245 particle Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical group CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- LFKXWKGYHQXRQA-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;iron Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LFKXWKGYHQXRQA-FDGPNNRMSA-N 0.000 description 1
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- PNXOJQQRXBVKEX-UHFFFAOYSA-N iron vanadium Chemical compound [V].[Fe] PNXOJQQRXBVKEX-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 238000001291 vacuum drying 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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
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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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- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to Fe2VO4An ordered mesoporous carbon composite material and application thereof, belonging to the technical field of sodium ion batteries. The composite material of the invention is made of Fe2VO4Is compounded with ordered mesoporous carbon, and the addition of the ordered mesoporous carbon can effectively inhibit Fe on one hand2VO4The self-agglomeration of the composite material relieves the volume expansion in the circulation process, ensures the integrity of the material structure in the circulation process, and has good circulation stability when used as a cathode material of a sodium ion battery; on the other hand, the conductivity and the specific surface area of the material can be improved, the sufficient contact with the electrolyte is ensured, and the material has good rate capability as a negative electrode material of a sodium-ion battery; in addition, the composite material is simple in preparation process, easy to operate, capable of realizing large-scale production and good in application prospect in the aspect of sodium ion battery cathode materials.
Description
Technical Field
The invention relates to a sodium ion battery cathode material, in particular to Fe2VO4An ordered mesoporous carbon composite material and application thereof, belonging to the technical field of sodium ion batteries.
Background
With the increasing environmental pollution, the development of new energy sources is urgent, but due to the transient characteristics of wind energy and solar energy, the development of large-scale energy storage devices with high performance and low cost is required. The lithium ion battery has already achieved commercial development, but due to the shortage of lithium resources and the large amount of mining, the cost of the lithium ion battery is increased, and the application of the lithium ion battery in large-scale energy storage is limited to a great extent. Sodium resources are abundant, cost is low, and sodium and lithium have the same chemical properties, so that the sodium-ion battery is considered to be the most potential selection for realizing next-generation large-scale energy storage.
Many negative electrode materials for sodium ion batteries have been studied, including carbon materials, transition metal oxides/sulfur/selenides, alloying materials, and organic materials, etc., wherein transition metal oxides are of interest to researchers due to their wide variety, low cost, etc. Iron vanadium double metal oxide (Fe)2VO4) The material has the characteristics of higher electronic/ionic conductivity, good reversible specific capacity, stable mechanical property and the like compared with single metal oxide, and has been applied to the negative electrode material of the sodium-ion battery. But Fe2VO4The conductive property of (2) is not high, agglomeration and the like are easy to occur, and the material is easy to crack or collapse during circulation, so that the capacity is quickly declined. Therefore, the structural integrity of the material in the circulation process needs to be guaranteed through reasonable design, and the sodium storage performance of the material is further improved.
Disclosure of Invention
For Fe2VO4The present invention provides a Fe that is deficient in sodium ion batteries2VO4The introduction of the ordered mesoporous carbon can improve the conductivity and effectively inhibit Fe2VO4The self-agglomeration of the material relieves the volume expansion in the circulation process, and the material used for the negative electrode material of the sodium-ion battery shows good circulation performance and rate capability.
The purpose of the invention is realized by the following technical scheme.
Fe2VO4The ordered mesoporous carbon composite material is prepared by adopting the following method:
(1) preparing a dispersion liquid containing an iron source, a vanadium source and ordered mesoporous carbon, transferring the dispersion liquid into a hydrothermal kettle, reacting for 10-25 h at 150-220 ℃, collecting a solid product of the hydrothermal reaction, washing and drying to obtain a composite material precursor;
(2) calcining the precursor of the composite material in the atmosphere of nitrogen or argon, and calcining for 3-12 h at 400-700 ℃ to obtain the composite material.
The iron source is ferric acetylacetonate, ferrous acetylacetonate, ferric chloride, ferric nitrate or ferric acetate; the vanadium source is vanadyl acetylacetonate or ammonium metavanadate; the ordered mesoporous carbon is CMK-3.
The solvent of the dispersion may be one capable of dissolving both the iron source and the vanadium source, and water, methanol or ethanol is preferable.
Preferably, the mass of the ordered mesoporous carbon in the composite material is Fe2VO45 to 10 percent of the mass.
Preferably, the molar ratio of the iron element in the iron source to the vanadium element in the vanadium source is (2-1): 1.
Preferably, the heating rate is 1-10 ℃/min during the calcination process.
Preferably, the specific preparation steps of the dispersion containing the iron source, the vanadium source and the ordered mesoporous carbon are as follows:
firstly, dispersing ordered mesoporous carbon in a solvent, then adding an iron source, and obtaining a dispersion liquid containing the iron source after the iron source is completely dissolved; dissolving a vanadium source in a solvent to obtain a solution containing the vanadium source; and adding the solution containing the vanadium source into the dispersion liquid containing the iron source, and uniformly mixing to obtain the dispersion liquid containing the iron source, the vanadium source and the ordered mesoporous carbon.
One kind of Fe of the present invention2VO4The application of the/ordered mesoporous carbon composite material in the cathode of the sodium ion battery.
Has the advantages that:
(1) the composite material of the invention is made of Fe2VO4Is compounded with ordered mesoporous carbon, and the addition of the ordered mesoporous carbon can effectively inhibit Fe on one hand2VO4The self-agglomeration of the composite material relieves the volume expansion in the circulation process, ensures the integrity of the material structure in the circulation process, and has good circulation stability when used as a cathode material of a sodium ion battery; on the other hand, the conductivity and the specific surface area of the material can be improved, the sufficient contact with the electrolyte is ensured, and the material has good rate capability as a sodium ion battery cathode material;
(2) the composite material is prepared by adopting a hydrothermal and calcination two-step method, the preparation process is simple, the operation is easy, the large-scale production can be realized, and the prepared composite material has good crystallinity and has good application prospect as a cathode material of a sodium-ion battery.
Drawings
FIG. 1 shows Fe prepared in example 12VO4X-ray diffraction (XRD) pattern of the/ordered mesoporous carbon composite material.
FIG. 2 shows Fe prepared in example 12VO4Raman diagram of ordered mesoporous carbon composite material.
FIG. 3 shows Fe prepared in example 12VO4Scanning Electron Microscope (SEM) images of/ordered mesoporous carbon composites.
FIG. 4 is Fe prepared by example 12VO4Cycle performance diagram of the battery assembled by the/ordered mesoporous carbon composite material under the current density of 100 mA/g.
FIG. 5 is Fe prepared by example 12VO4The rate performance diagram of the battery assembled by the ordered mesoporous carbon composite material.
FIG. 6 is Fe prepared by example 22VO4Cycle performance diagram of the battery assembled by the/ordered mesoporous carbon composite material under the current density of 100 mA/g.
Detailed Description
The present invention is further illustrated by the following detailed description, wherein the processes are conventional unless otherwise specified, and the starting materials are commercially available from a public source without further specification.
The battery assembly steps are as follows: fe prepared in example2VO4Mixing the ordered mesoporous carbon composite material, carbon black and carboxymethyl cellulose according to the mass ratio of 7:2:1, adding a proper amount of water to prepare slurry, coating the slurry on a copper foil, drying the copper foil in a vacuum drying oven at 80 ℃ for 12 hours, and cutting the dried copper foil into a wafer serving as a negative electrode; sodium metal as counter electrode and reference electrode, Whatman glass fiber as diaphragm, electrolyte composed of ethylene carbonate and diethyl carbonate (1:1, v/v) and 5% fluoroethylene carbonate, and glove boxThe 2032 type button cell is assembled.
Example 1
(1) Dispersing 25mg of CMK-3 into 40mL of ethanol, performing ultrasonic dispersion for 30min, then adding 2mmol of ferric acetylacetonate, and stirring to completely dissolve the ferric acetylacetonate to obtain a dispersion liquid containing an iron source; adding 1mmol of vanadyl acetylacetonate into 40mL of ethanol and dissolving to obtain a solution containing a vanadium source; adding the solution containing the vanadium source into the dispersion liquid containing the iron source, and uniformly stirring to obtain the dispersion liquid containing the iron source, the vanadium source and the ordered mesoporous carbon;
(2) pouring a dispersion liquid containing an iron source, a vanadium source and ordered mesoporous carbon into a 100mL polytetrafluoroethylene hydrothermal kettle, reacting for 12h at 180 ℃, cooling to room temperature, centrifuging, collecting a solid product, washing with ethanol for multiple times, and drying to obtain a composite material precursor;
(4) uniformly dispersing the composite material precursor in a crucible, putting the crucible into a tube furnace, heating to 500 ℃ at the heating rate of 5 ℃/min under the argon atmosphere, preserving heat for 5h, and cooling along with the furnace to obtain Fe2VO4Ordered mesoporous carbon composite material.
As can be seen from FIG. 1, the diffraction peak and Fe of the prepared composite material2VO4(JCPDS #75-1519) was matched by a standard spectrum, indicating that the composite material prepared contained Fe2VO4(ii) a The CMK-3 diffraction peak in the XRD pattern was not detected because the peak was masked due to the lower content. In the Raman spectrum in FIG. 2, Fe was detected2VO4While detecting the D peak (1320 m)-1) And G peak (1600 m)-1) The presence of CMK-3 was demonstrated, indicating that Fe was successfully prepared2VO4Ordered mesoporous carbon composite material.
As can be seen from the SEM photograph of FIG. 3, the prepared composite material contained CMK-3 having a rod-like structure and Fe having a particle structure2VO4，Fe2VO4The particles have a size below 100nm and are dispersively adhered to the surface of CMK-3, while the addition of CMK-3 avoids Fe2VO4The particles agglomerate to form a bulk structure that provides sufficient space to relieve swelling during the cycle.
The prepared composite material is assembled into a battery, and the cycle performance test is carried out under the current density of 100 mA/g. As can be seen from the test results in FIG. 4, the first cycle specific discharge capacity was 542mA · h/g; the specific discharge capacity of 300 cycles is 219 mA.h/g, the coulombic efficiency is close to 100%, and the capacity retention rate is about 81% (the specific discharge capacity of the 300 th cycle/the specific discharge capacity of the 2 nd cycle), which indicates that the prepared composite material shows stable cycle performance in a sodium-ion battery.
The prepared composite material is assembled into a battery to be subjected to rate performance test, and the test result is shown in fig. 4. According to the test results, the specific discharge capacity of the battery is 229mA · h/g after the battery is cycled for 10 weeks under the current density of 0.1A/g, the specific discharge capacity of the battery is 138mA · h/g after the battery is cycled for 10 weeks under the current density of 3.2A/g, and the specific discharge capacity of the battery is 217mA · h/g after the battery is cycled for 10 weeks under the current density of 0.1A/g again, which indicates that the prepared composite material has excellent rate performance.
Example 2
(1) Dispersing 15mg of CMK-3 into 40mL of methanol, performing ultrasonic dispersion for 30min, then adding 1mmol of ferric nitrate, and stirring to completely dissolve the ferric nitrate to obtain a dispersion liquid containing an iron source; adding 1mmol of ammonium metavanadate into 40mL of methanol and dissolving to obtain a solution containing a vanadium source; adding the solution containing the vanadium source into the dispersion liquid containing the iron source, and uniformly stirring to obtain the dispersion liquid containing the iron source, the vanadium source and the ordered mesoporous carbon;
(2) pouring a dispersion liquid containing an iron source, a vanadium source and ordered mesoporous carbon into a 100mL polytetrafluoroethylene hydrothermal kettle, reacting for 10h at 200 ℃, cooling to room temperature, centrifuging to collect a solid product, washing with methanol for multiple times, and drying to obtain a composite material precursor;
(4) uniformly dispersing a composite material precursor in a crucible, putting the crucible into a tube furnace, heating to 600 ℃ at a heating rate of 2 ℃/min under the argon atmosphere, preserving heat for 4h, and cooling along with the furnace to obtain Fe2VO4Ordered mesoporous carbon composite material.
According to the characterization results of XRD and Raman, the prepared composite material contains Fe2VO4And CMK-3. Root of herbaceous plantAccording to the characterization result of SEM, the prepared composite material contains CMK-3 with a rod-shaped structure and Fe with a particle structure2VO4And is of Fe2VO4The particles are dispersively adhered to the surface of the CMK-3.
The prepared composite material is assembled into a battery, and the cycle performance test is carried out under the current density of 100 mA/g. As can be seen from the test results shown in FIG. 6, the first cycle specific discharge capacity was 400mA · h/g; the specific discharge capacity of the composite material after 300 cycles is 189mA · h/g, the average coulombic efficiency of the composite material after 300 cycles is 99.3%, and the capacity is kept stable in the cycle from 50 cycles to 300 cycles, which shows that the prepared composite material has good reversibility.
The prepared composite material is assembled into a battery to be subjected to rate performance test, and according to test results, the specific discharge capacity of the battery is 242mA · h/g after the battery is cycled for 10 weeks under the current density of 0.1A/g, the specific discharge capacity of the battery is 102mA · h/g after the battery is cycled for 10 weeks under the current density of 3.2A/g, and the specific discharge capacity of the battery is 198mA · h/g after the battery is cycled for 10 weeks under the current density of 0.1A/g again, which indicates that the prepared composite material has excellent rate performance.
In summary, the above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. Fe2VO4The ordered mesoporous carbon composite material is characterized in that: the composite material is prepared by adopting the following method,
(1) preparing a dispersion liquid containing an iron source, a vanadium source and ordered mesoporous carbon, transferring the dispersion liquid into a hydrothermal kettle, reacting for 10-25 h at 150-220 ℃, collecting a solid product of the hydrothermal reaction, washing and drying to obtain a composite material precursor;
(2) calcining the composite material precursor in nitrogen or argon atmosphere, and calcining for 3-12 h at 400-700 ℃ to obtain the composite material;
wherein the iron source is iron acetylacetonateFerrous acetylacetonate, ferric chloride, ferric nitrate or ferric acetate; the vanadium source is vanadyl acetylacetonate or ammonium metavanadate; the ordered mesoporous carbon is CMK-3; in the composite material, the mass of the ordered mesoporous carbon is Fe2VO45 to 10 percent of the mass.
2. Fe of claim 12VO4The ordered mesoporous carbon composite material is characterized in that: in the step (1), the solvent of the dispersion liquid is water, methanol or ethanol.
3. Fe of claim 12VO4The ordered mesoporous carbon composite material is characterized in that: the molar ratio of the iron element in the iron source to the vanadium element in the vanadium source is (2-1): 1.
4. Fe of claim 12VO4The ordered mesoporous carbon composite material is characterized in that: in the calcining process, the heating rate is 1-10 ℃/min.
5. Fe of claim 12VO4The ordered mesoporous carbon composite material is characterized in that: the specific preparation steps of the dispersion liquid containing the iron source, the vanadium source and the ordered mesoporous carbon are as follows,
firstly, dispersing ordered mesoporous carbon in a solvent, then adding an iron source, and obtaining a dispersion liquid containing the iron source after the iron source is completely dissolved; dissolving a vanadium source in a solvent to obtain a solution containing the vanadium source; and adding the solution containing the vanadium source into the dispersion liquid containing the iron source, and uniformly mixing to obtain the dispersion liquid containing the iron source, the vanadium source and the ordered mesoporous carbon.
6. Fe as claimed in any one of claims 1 to 52VO4The application of the/ordered mesoporous carbon composite material in the cathode of the sodium ion battery.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107579231A (en) * | 2017-09-08 | 2018-01-12 | 安徽玄同工业设计有限公司 | The preparation method of three-dimensional graphite alkenyl ferric vandate |
| CN108539185A (en) * | 2018-05-24 | 2018-09-14 | 中南大学 | A kind of lithium or anode material of lithium-ion battery and preparation method thereof |
| CN110867578A (en) * | 2019-11-21 | 2020-03-06 | 江苏理工学院 | Sodium ion battery and preparation method and application thereof |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000124082A (en) * | 1998-10-14 | 2000-04-28 | Fuji Electric Co Ltd | Energy-storing element and manufacture thereof |
| JP4770069B2 (en) * | 2000-06-13 | 2011-09-07 | 株式会社Ｇｓユアサ | Positive electrode active material for secondary battery, method for producing the same, and non-aqueous electrolyte secondary battery including the same |
| WO2009074353A1 (en) * | 2007-12-12 | 2009-06-18 | Centre National De La Recherche Scientifique (C.N.R.S) | Iron-doped vanadium(v) oxides |
| CN102299303B (en) * | 2011-09-01 | 2013-12-11 | 深圳科雷拉能源科技有限公司 | Method for preparing lithium iron phosphate-lithium vanadium phosphate cathode material of lithium ion battery |
| CN102386382A (en) * | 2011-11-03 | 2012-03-21 | 大连理工大学 | CMK-5 type mesoporous carbon-nano inorganic substance composite material, preparation method and application thereof |
| CN104701496A (en) * | 2013-12-05 | 2015-06-10 | 江南大学 | SnO2/CMK-3 nanometer composite lithium-ion battery negative electrode material preparation method |
| CN103943826B (en) * | 2014-04-21 | 2017-01-18 | 西安交通大学 | Preparation method of metal oxide/sulfide and ordered mesoporous carbon composite energy-storage material |
| CN104157858B (en) * | 2014-08-12 | 2016-08-24 | 武汉理工大学 | Classifying porous ferroso-ferric oxide/graphene nano line and its preparation method and application |
| CN106011456B (en) * | 2016-08-02 | 2017-12-08 | 北京科技大学 | A kind of method that vanadium by Rock coal containing alum is enriched with and vanadium enrichment mutually regulates and controls |
| CN107082453B (en) * | 2017-03-24 | 2019-01-15 | 哈尔滨工程大学 | The preparation of hydrated iron barium oxide as water system Magnesium ion battery negative electrode material and application method |
| CN107512740B (en) * | 2017-08-29 | 2019-01-18 | 合肥国轩电池材料有限公司 | A kind of lithium ion battery negative material FeVO4The preparation method of nano wire |
| CN107670683B (en) * | 2017-10-16 | 2020-04-10 | 陕西科技大学 | FeVO4@g-C3N4Core-shell structure heterojunction photocatalyst and preparation method thereof |
| CN108161026B (en) * | 2017-12-13 | 2021-09-28 | 东南大学 | Preparation method and application of supported bimetal nano material |
| CN108374082B (en) * | 2018-02-08 | 2019-06-07 | 北京科技大学 | A method of vanadium grade in vanadium concentrate is improved by oxidation processes-magnetic separation separation |
-
2020
- 2020-05-26 CN CN202010457758.3A patent/CN111900389B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107579231A (en) * | 2017-09-08 | 2018-01-12 | 安徽玄同工业设计有限公司 | The preparation method of three-dimensional graphite alkenyl ferric vandate |
| CN108539185A (en) * | 2018-05-24 | 2018-09-14 | 中南大学 | A kind of lithium or anode material of lithium-ion battery and preparation method thereof |
| CN110867578A (en) * | 2019-11-21 | 2020-03-06 | 江苏理工学院 | Sodium ion battery and preparation method and application thereof |
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