CN113036102B - Molybdenum selenide composite carbonized common sowthistle herb flower crown hair electrode material for sodium ion battery - Google Patents
Molybdenum selenide composite carbonized common sowthistle herb flower crown hair electrode material for sodium ion battery Download PDFInfo
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- CN113036102B CN113036102B CN202110239510.4A CN202110239510A CN113036102B CN 113036102 B CN113036102 B CN 113036102B CN 202110239510 A CN202110239510 A CN 202110239510A CN 113036102 B CN113036102 B CN 113036102B
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- ion battery
- carbonized
- powder
- common sowthistle
- flower crown
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 34
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 244000113428 Sonchus oleraceus Species 0.000 title claims abstract description 26
- 235000006745 Sonchus oleraceus Nutrition 0.000 title claims abstract description 26
- 239000007772 electrode material Substances 0.000 title claims abstract description 18
- 210000004209 hair Anatomy 0.000 title claims abstract description 17
- MHWZQNGIEIYAQJ-UHFFFAOYSA-N molybdenum diselenide Chemical compound [Se]=[Mo]=[Se] MHWZQNGIEIYAQJ-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 239000002131 composite material Substances 0.000 title claims abstract description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 229910004619 Na2MoO4 Inorganic materials 0.000 claims abstract description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052786 argon Inorganic materials 0.000 claims abstract description 4
- 238000007865 diluting Methods 0.000 claims abstract description 4
- 230000007935 neutral effect Effects 0.000 claims abstract description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 4
- 229910052573 porcelain Inorganic materials 0.000 claims abstract description 4
- 239000011684 sodium molybdate Substances 0.000 claims abstract description 4
- 238000000967 suction filtration Methods 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims abstract description 3
- 238000010000 carbonizing Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims 1
- 238000007789 sealing Methods 0.000 claims 1
- 238000005054 agglomeration Methods 0.000 abstract description 4
- 230000002776 aggregation Effects 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 3
- 235000015393 sodium molybdate Nutrition 0.000 abstract description 3
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 abstract description 3
- 229910001868 water Inorganic materials 0.000 abstract description 3
- 239000011734 sodium Substances 0.000 description 6
- 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 5
- 239000003792 electrolyte Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000012983 electrochemical energy storage Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 241000488874 Sonchus Species 0.000 description 1
- 235000008132 Sonchus arvensis ssp. uliginosus Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000007833 carbon precursor Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- 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
- H01M4/36—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
-
- 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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
-
- 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
Abstract
The invention provides a molybdenum selenide composite carbonized common sowthistle herb flower crown hair used as an electrode material of a sodium ion battery, wherein common sowthistle herb flower crown hair powder is put into a porcelain boat and is heated to 500 ℃ for two hours under the protection of argon gas to be carbonized, so that the carbonized common sowthistle herb flower crown hair material is obtained; dissolving Na2MoO4 in deionized water, adding selenium powder, and dissolving with N2H 2. H2O; slowly adding dimethylformamide to obtain a black solution, transferring the black solution to a polytetrafluoroethylene reaction kettle, and heating the reaction kettle for 12 hours at 200 ℃ in a sealed manner; and after the reaction kettle is naturally cooled, taking out the solution, diluting the solution with deionized water until the pH value is neutral, performing suction filtration to obtain powder, and drying the powder in a 60 ℃ drying oven for 12 hours to obtain the molybdenum selenide composite carbonized common sowthistle herb flower crown electrode material. The invention makes up the defects of low rate performance, easy agglomeration, poor electronic and ionic conductivity and the like of the sodium-ion battery material, and solves the problems of poor cycle life, low energy density and the like of the sodium-ion battery.
Description
Technical Field
The invention relates to an electrode material for a sodium-ion battery, in particular to an electrode material for a sodium-ion battery, which is prepared by compounding molybdenum selenide and carbonized common sowthistle herb flower crowns.
Background
The fields of new energy automobiles and the like are rapidly developing, and in order to meet the future large-scale electrochemical energy storage requirements and the increasing lithium battery cost, the development and design of a cheap and stable energy storage device is urgent. Sodium ion batteries have received much attention for their excellent electrochemical performance and abundant Na resources. The cathode and anode of a conventional sodium ion battery are both slow diffusion reactions, which results in poor power density and cycling stability. The structure of the sodium ion battery is similar to that of the lithium ion battery, the sodium ion battery is composed of a positive electrode, a negative electrode, a diaphragm and electrolyte, the energy storage mechanism of the sodium ion battery is also similar to that of the lithium ion battery, and the electrochemical energy storage and release are realized on the basis of the migration of sodium/lithium ions between the positive electrode and the negative electrode. During charging, sodium ions are separated from the positive electrode crystal lattice and migrate to the surface of the negative electrode through the electrolyte to be embedded into the negative electrode crystal lattice, meanwhile, electrons flow from the positive electrode to the negative electrode in an external circuit, the potential of the negative electrode is reduced, and the voltage difference between the positive electrode and the negative electrode is increased, so that the charging of the sodium ion battery is realized. During discharging, the process is opposite, sodium ions are extracted from the negative electrode and are embedded into the positive electrode again after passing through the electrolyte, electrons flow from the negative electrode to the positive electrode of the external circuit to supply power for equipment connected with the external circuit, and therefore the sodium ion battery finishes discharging.
The sodium ion battery performance is mainly influenced by factors such as electrode materials and electrolyte components, and the preparation of the negative electrode material is an important research direction for improving the performance of the sodium ion battery. The transition metal sulfide and selenide can be used as an ideal anode material to be applied to the sodium-ion battery due to the advantages of high specific capacity, good economy and the like. See in particular the documents Han M H, Gonzalo E, Singh G, et al.A complex review of Sodium layered oxides, powerfull reagents for Na-Ion Batteries [ J ]. Energy Environ Sci 2015,8(1):81-102. and Xiang X, Zhang K, Chen J.Recent Advances and Prospectra of Cathode Materials for Sodium-Ion Batteries [ J ]. Advanced Materials 2015,27(36): 5343-64.
Disclosure of Invention
The invention aims to provide an electrode material of a molybdenum selenide composite carbonized sowthistle herb flower crown for a sodium ion battery, overcomes the defects of low rate performance, easy agglomeration, poor electron and ion conductivity and the like of a sodium ion battery material, and solves the problems of poor cycle life, low energy density and the like of the sodium ion battery.
The purpose of the invention is realized by the following steps:
1g of the powder of the common sowthistle herb flower crown hairs is put into a porcelain boat and is carbonized for two hours at the temperature rise rate of 2 ℃/min to 500 ℃ under the protection of argon, so that the carbonized common sowthistle herb flower crown hair material is obtained. 0.1532g Na2MoO4 was dissolved in 5ml deionized water, 0.1g selenium powder was added and dissolved in 5ml N2H 2. H2O. Then 20ml of Dimethylformamide (DMF) was slowly added to obtain a black solution, which was transferred to a 50ml polytetrafluoroethylene reaction vessel, and the reaction vessel was sealed and heated at 200 ℃ for 12 hours. And after the reaction kettle is naturally cooled, taking out the solution, diluting the solution with deionized water until the pH value is neutral, performing suction filtration to obtain powder, and drying the powder in a 60 ℃ drying oven for 12 hours to obtain the molybdenum selenide composite carbonized common sowthistle herb flower crown electrode material.
The essence of the invention is seleniumMolybdenum carbide composite carbonized common sowthistle herb flower crown hair is taken as an anode material, metal sodium is taken as a cathode material, a polypropylene film is taken as a battery diaphragm, and the concentration of the metal sodium is 1 mol.L-1NaClO (sodium chloride)4And the electrolyte is used for assembling a sodium ion battery device to obtain the capacity and the cycle life of the sodium ion battery.
Compared with the prior art, the invention has the beneficial effects that:
the natural sonchus oleraceus flower crown hair has a hollow tubular structure, and the molybdenum selenide composite carbonized sonchus oleraceus flower crown hair electrode material with a large specific surface can be prepared after carbonization. Overcomes the defects of easy agglomeration and poor conductivity of the pure molybdenum selenide material. The molybdenum selenide composite carbonized common sowthistle herb flower crown electrode material is applied to a sodium ion battery, and the large surface area and surface functional groups of the carbonized common sowthistle herb flower crown provide rich redox centers and ion transmission paths of non-bulk phase diffusion, so that good rate capability is ensured. And the volume expansion of the electrode material can be prevented, and the electrode pulverization and agglomeration can be prevented, so that the stable cycle performance of the sodium-ion battery can be realized. The molybdenum selenide composite carbonized common sow thistle flower crown hair electrode is used as an electrode material of the sodium ion battery, the common sow thistle carbon precursor is rich in reserve and low in price, and the sodium ion battery is high in capacity, rate capability, energy density and cycling stability.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments.
A molybdenum selenide composite carbonized common sowthistle flower crown hair material used as an electrode material of a sodium ion battery is prepared by putting 1g of common sowthistle flower crown hair powder into a porcelain boat, heating to 500 ℃ at a heating rate of 2 ℃/min under the protection of argon gas, and carbonizing for two hours to obtain the carbonized common sowthistle flower crown hair material. 0.1532g Na2MoO4 was dissolved in 5ml deionized water, 0.1g selenium powder was added and dissolved in 5ml N2H 2. H2O. Then 20ml of Dimethylformamide (DMF) was slowly added to obtain a black solution, which was transferred to a 50ml polytetrafluoroethylene reaction vessel, and the reaction vessel was sealed and heated at 200 ℃ for 12 hours. And after the reaction kettle is naturally cooled, taking out the solution, diluting the solution with deionized water until the pH value is neutral, performing suction filtration to obtain powder, and drying the powder in a 60 ℃ drying oven for 12 hours to obtain the molybdenum selenide composite carbonized common sowthistle herb flower crown electrode material.
Molybdenum selenide composite carbonized common sowthistle flower crown electrode material is used as a cathode material, metal sodium is used as an anode material, a polypropylene film is used as a battery diaphragm, and 1 mol.L-1NaClO (NaClO)4DMC, EC and FEC are mixed as organic electrolyte to assemble sodium ion battery half cell with 1 A.g-1The current density of (2) is obtained to be 118mAh g-1The capacity retention ratio after 500 cycles is 86%.
Claims (1)
1. A preparation method of a molybdenum selenide composite carbonized common sowthistle herb flower crown hair electrode material for a sodium ion battery is characterized by comprising the following steps:
putting 1g of the powder of the common sowthistle herb flower crown hairs into a porcelain boat, heating to 500 ℃ at a heating rate of 2 ℃/min under the protection of argon gas, and carbonizing the powder for two hours to obtain a carbonized common sowthistle herb flower crown hair material;
0.1532g of Na2MoO4Dissolving in 5ml deionized water, adding 0.1g selenium powder and 5ml N2H2•H2Dissolving O, slowly adding 20ml of Dimethylformamide (DMF) to obtain a black solution, transferring the black solution to a 50ml of polytetrafluoroethylene reaction kettle, sealing the reaction kettle, heating at 200 ℃ for 12h, naturally cooling the reaction kettle, taking out the solution, diluting the solution with deionized water until the pH value is neutral, performing suction filtration to obtain powder, and drying in a 60 ℃ oven for 12h to obtain the molybdenum selenide composite carbonized common sowthistle herb crown electrode material.
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|---|---|---|---|
| CN202110239510.4A CN113036102B (en) | 2021-03-04 | 2021-03-04 | Molybdenum selenide composite carbonized common sowthistle herb flower crown hair electrode material for sodium ion battery |
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| CN202110239510.4A CN113036102B (en) | 2021-03-04 | 2021-03-04 | Molybdenum selenide composite carbonized common sowthistle herb flower crown hair electrode material for sodium ion battery |
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Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4604334A (en) * | 1985-10-30 | 1986-08-05 | Bell Communications Research, Inc. | Mo6 Se6 solid state electrode for secondary lithium batteries |
| CN105006570B (en) * | 2015-06-10 | 2017-03-29 | 中南大学 | A kind of sodium-ion battery selenizing molybdenio anode material and preparation method thereof |
| CN105742602B (en) * | 2016-03-27 | 2018-07-20 | 华南理工大学 | A kind of sodium-ion battery cathode Sn/MoS2/ C composite and preparation method thereof |
| CN105810447A (en) * | 2016-04-29 | 2016-07-27 | 陕西科技大学 | Preparation method of porous spherical biological carbon and application |
| CN106744951A (en) * | 2017-03-21 | 2017-05-31 | 哈尔滨工程大学 | A kind of quick method for preparing activated carbon |
| CN109786682A (en) * | 2018-06-20 | 2019-05-21 | 信阳师范学院 | 12 face nucleome anode material of lithium-ion battery of a kind of two selenizing molybdenum@nitrogen-doped carbon and preparation method thereof, sodium-ion battery |
| CN109742361B (en) * | 2019-01-08 | 2021-09-28 | 福建师范大学 | Preparation method and application of composite sodium-ion battery negative electrode material |
| CN110620226A (en) * | 2019-10-15 | 2019-12-27 | 中国计量大学 | Preparation method of nitrogen and boron co-doped carbon fiber loaded molybdenum selenide electrode material |
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