CN117650231A - Molybdenum-based oxide, preparation method thereof, anode material and water-based zinc ion battery - Google Patents
Molybdenum-based oxide, preparation method thereof, anode material and water-based zinc ion battery Download PDFInfo
- Publication number
- CN117650231A CN117650231A CN202311508463.4A CN202311508463A CN117650231A CN 117650231 A CN117650231 A CN 117650231A CN 202311508463 A CN202311508463 A CN 202311508463A CN 117650231 A CN117650231 A CN 117650231A
- Authority
- CN
- China
- Prior art keywords
- molybdenum
- based oxide
- zinc
- manganese
- source
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 72
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000011733 molybdenum Substances 0.000 title claims abstract description 65
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000010405 anode material Substances 0.000 title description 3
- 239000007773 negative electrode material Substances 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 3
- 239000012298 atmosphere Substances 0.000 claims description 28
- 239000011701 zinc Substances 0.000 claims description 23
- 229910052725 zinc Inorganic materials 0.000 claims description 19
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 16
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 14
- 239000011240 wet gel Substances 0.000 claims description 12
- 239000011572 manganese Substances 0.000 claims description 11
- 229910052748 manganese Inorganic materials 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000002738 chelating agent Substances 0.000 claims description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 4
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 claims description 4
- 239000011656 manganese carbonate Substances 0.000 claims description 4
- 235000006748 manganese carbonate Nutrition 0.000 claims description 4
- 229940093474 manganese carbonate Drugs 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 4
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- VASIZKWUTCETSD-UHFFFAOYSA-N oxomanganese Chemical compound [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 claims description 4
- 239000011667 zinc carbonate Substances 0.000 claims description 4
- 235000004416 zinc carbonate Nutrition 0.000 claims description 4
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- HYZQBNDRDQEWAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;manganese(3+) Chemical compound [Mn+3].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O HYZQBNDRDQEWAN-LNTINUHCSA-N 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 description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- TYTHZVVGVFAQHF-UHFFFAOYSA-N manganese(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Mn+3].[Mn+3] TYTHZVVGVFAQHF-UHFFFAOYSA-N 0.000 claims description 2
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 claims description 2
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims 1
- 150000002500 ions Chemical class 0.000 abstract description 3
- 230000001351 cycling effect Effects 0.000 abstract description 2
- 238000000227 grinding Methods 0.000 description 11
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 229960002303 citric acid monohydrate Drugs 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- 239000011149 active material Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000003980 solgel method Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 4
- 229960001763 zinc sulfate Drugs 0.000 description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 229960004106 citric acid Drugs 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a molybdenum-based oxide, a preparation method thereof, a negative electrode material and a water-based zinc ion battery. The chemical formula of the molybdenum-based oxide is ZnMnMo 3 O 8 Belongs to a hexagonal system, and has unit cell parameters ofα=β=90°, γ=120°. The molybdenum-based oxide is rich in zinc ions, can provide sufficient working ions for the water-based zinc ion battery by taking the molybdenum-based oxide as a negative electrode material, has excellent cycling stability and excellent electrochemical performance, and is suitable for large-scale popularization and application.
Description
Technical Field
The invention relates to the technical field of water-based zinc ion batteries, in particular to a molybdenum-based oxide, a preparation method thereof, a negative electrode material and a water-based zinc ion battery.
Background
The lithium ion battery has the advantages of high energy density, long service life and the like, and is widely applied to the fields of mobile equipment, electric automobiles, energy storage systems and the like. However, the lithium ion battery may have fire and explosion under the conditions of overcharge/discharge, high-temperature environment, and the like, and has a large potential safety hazard, and the production cost of the lithium ion battery will be higher and higher along with the large-area popularization and application of the lithium ion battery due to the limited reserve of lithium resources on the earth. Accordingly, researchers are continually exploring electrochemical energy storage systems based on more abundant elements on earth, such as: magnesium ion batteries, zinc ion batteries, sodium ion batteries, and the like.
The aqueous zinc ion battery has advantages such as low cost and high safety, and has been attracting attention in recent years. Zinc has lower activity than lithium, so that the zinc ion battery can use aqueous solution as electrolyte, and zinc has rich reserve in crust and wider application prospect. Compared with a lithium ion battery and a sodium ion battery (both the lithium ion battery and the sodium ion battery adopt organic electrolyte), the water-based zinc ion battery has the advantages that the solvent is easier to obtain, the cost is lower, and the water is safer as the solvent of the electrolyte. However, zinc metal cathodes are commonly used in the conventional water-based zinc ion batteries, and zinc dendrite growth during charge and discharge cycles can cause problems of short circuit, stripping and deactivation of the cathodes and the like, and the zinc metal cathodes are easy to be corroded and dissolved in electrolyte for a long time to generate hydrogen evolution phenomenon, so that the problems of low utilization rate of cathode materials, poor battery cycle performance and the like can be caused, and the commercialized application of the water-based zinc ion batteries is severely restricted.
Therefore, the development of the anode material with more excellent comprehensive performance has very important significance.
Disclosure of Invention
The invention aims to provide a molybdenum-based oxide, a preparation method thereof, a negative electrode material and an aqueous zinc ion battery.
The technical scheme adopted by the invention is as follows:
molybdenum-based oxide with chemical formula of ZnMnMo 3 O 8 Belongs to a hexagonal system, and has unit cell parameters of α＝β＝90°，γ＝120°。
A method of preparing a molybdenum-based oxide as described above comprising the steps of:
1) Dispersing a zinc source, a manganese source, a molybdenum source and an organic chelating agent in water to prepare sol, and heating to evaporate water to obtain wet gel;
2) Drying the wet gel obtained in the step 1) to obtain xerogel, and presintering to obtain a presintering product;
3) And (3) placing the presintered product in the step (2) in a reducing atmosphere for sintering to obtain the molybdenum-based oxide.
Preferably, a method for preparing a molybdenum-based oxide as described above comprises the steps of:
1) Dispersing a zinc source, a manganese source, a molybdenum source and an organic chelating agent in water to prepare sol, and heating to evaporate water to obtain wet gel;
2) Drying the wet gel obtained in the step 1) to obtain xerogel, grinding into powder, presintering, naturally cooling, and grinding to obtain presintering products;
3) And (3) grinding the presintered product in the step (2) again, then placing the ground presintered product in a reducing atmosphere for sintering, and naturally cooling to obtain the molybdenum-based oxide.
Preferably, step 1) the zinc is synthesised as zinc acetate (Zn (CH) 3 COO) 2 ·2H 2 O), zinc carbonate (ZnCO) 3 ·7H 2 O)、Zinc nitrate (Zn (NO) 3 ) 2 ) At least one of them.
Preferably, the manganese source of step 1) is manganese acetate (Mn (CH) 3 COO) 2 ·4H 2 O), manganese carbonate (MnCO) 3 ·H 2 O), manganese acetylacetonate (C) 10 H 14 MnO 4 ) Manganese dioxide (MnO) 2 ) Manganese monoxide (MnO), manganese sesquioxide (Mn) 2 O 3 ) At least one of them.
Preferably, the molybdenum source of step 1) is ammonium molybdate (Mo 7 N 6 H 24 O 24 ·4H 2 O), molybdenum acetylacetonate (C) 10 H 14 MoO 6 ) Molybdic acid (H) 2 MoO 4 ) Molybdenum trioxide (MoO) 3 ) Molybdenum dioxide (MoO) 2 ) At least one of them.
Preferably, the organic chelating agent of step 1) is citric acid (C) 6 H 8 O 7 ) Ascorbic acid (C) 6 H 8 O 6 ) Oxalic acid (H) 2 C 2 O 4 ) At least one of them.
Preferably, the zinc source, the manganese source and the molybdenum source in the step 1) are added according to a mole ratio of Zn, mn and Mo of 1:1:3.
Preferably, the molar ratio of the molybdenum source to the organic chelating agent in the step 1) is 1:4-9.
Preferably, the evaporation of water in step 1) is carried out at a temperature of 60 to 100 ℃.
Preferably, the drying in step 2) is carried out at a temperature of 70℃to 150 ℃.
Preferably, the presintering in the step 2) is carried out at the temperature of 200-400 ℃ for 3-6 hours.
Preferably, the pre-firing in step 2) is performed in an air atmosphere, a reducing atmosphere or a protective atmosphere.
Preferably, the reducing atmosphere is Ar-H 2 Mixed atmosphere, N 2 -H 2 A mixed atmosphere, a hydrogen atmosphere and an ammonia atmosphere.
Preferably, the protective atmosphere is nitrogen (N 2 ) ArgonGas (Ar), carbon dioxide (CO) 2 ) One of helium (He).
Preferably, the sintering in the step 3) is performed at the temperature of 600-800 ℃ for 8-12 hours.
Preferably, the reducing atmosphere in step 3) is Ar-H 2 Mixed atmosphere, N 2 -H 2 A mixed atmosphere, a hydrogen atmosphere and an ammonia atmosphere.
A negative electrode material comprising the above molybdenum-based oxide.
An aqueous zinc ion battery comprising the negative electrode material.
The beneficial effects of the invention are as follows: the molybdenum-based oxide is rich in zinc ions, can provide sufficient working ions for the water-based zinc ion battery by taking the molybdenum-based oxide as a negative electrode material, has excellent cycling stability and excellent electrochemical performance, and is suitable for large-scale popularization and application.
Specifically:
1) Molybdenum-based oxide (ZnMnMo) 3 O 8 ) The zinc ion-rich cathode is rich in zinc ions, can provide working ions for the water-based zinc ion battery, and avoids problems of zinc dendrite, hydrogen evolution, side reaction and the like caused by using a zinc metal cathode, so that the circulation stability of the water-based zinc ion battery can be improved;
2) The molybdenum-based oxide of the invention has stable Mo 3 O 8 The layered structure is very stable in air, and is beneficial to transportation and preservation;
3) When the molybdenum-based oxide is prepared, the organic chelating agent is carbonized in the sintering process, and a conductive network can be formed among material particles, so that the conductivity and electrochemical activity of the material can be further improved;
4) The molybdenum-based oxide is prepared by a sol-gel method, can synthesize high-purity active materials at a lower temperature, has low manufacturing cost and improves the safety of the synthesis process;
5) The molybdenum-based oxide provided by the invention can be used as a negative electrode material to show excellent cycle performance and wide operating voltage window in a water-based zinc ion battery.
Drawings
Fig. 1 is an SEM image and EDS spectrum of the molybdenum-based oxide of example 1.
Fig. 2 is an XRD pattern of the molybdenum-based oxide of example 1.
Fig. 3 is a charge-discharge curve of an aqueous zinc ion battery assembled from the molybdenum-based oxide of example 1.
Fig. 4 is a graph showing the results of the cycle performance test of the aqueous zinc ion battery assembled from the molybdenum-based oxide of example 1.
Fig. 5 is an XRD pattern of the molybdenum-based oxide of example 2.
Fig. 6 is a charge-discharge curve of an aqueous zinc ion battery assembled from the molybdenum-based oxide of example 2.
Fig. 7 is an XRD pattern of the molybdenum-based oxide of example 3.
Fig. 8 is a charge-discharge curve of an aqueous zinc ion battery assembled from the molybdenum-based oxide of example 3.
Detailed Description
The invention is further illustrated and described below in connection with specific examples.
Example 1:
a molybdenum-based oxide, which is prepared by the following steps:
1) Zn (CH) 3 COO) 2 ·2H 2 O、Mn(CH 3 COO) 2 ·4H 2 O and Mo 7 N 6 H 24 O 24 ·4H 2 O is added into deionized water according to the mole ratio of Zn, mn and Mo of 1:1:3, stirred for 30min at the constant temperature of 90 ℃, and then mixed according to Mo 7 N 6 H 24 O 24 ·4H 2 Adding citric acid monohydrate into the mixture according to the mol ratio of O to citric acid monohydrate of 1:7 to prepare sol, and continuously stirring until deionized water is evaporated to dryness to obtain wet gel;
2) Adding the wet gel obtained in the step 1) into an oven to bake for 5 hours at 150 ℃ to prepare xerogel, grinding into powder, presintering for 4 hours in argon atmosphere at the temperature of 350 ℃, naturally cooling, and grinding to obtain a presintering product;
3) Step 2) Is ground again and then placed in H 2 Ar Mixed atmosphere (H) 2 Is sintered for 10 hours at 750 ℃ in the volume fraction of 5 percent) and then naturally cooled to obtain molybdenum-based oxide (ZnMnMo) 3 O 8 )。
Performance test:
1) The molybdenum-based oxide (ZnMnMo) 3 O 8 ) The Scanning Electron Microscope (SEM) and EDS spectra are shown in fig. 1 (a and b are SEM images of different magnifications, c is SEM image of selected region and EDS spectra).
As can be seen from fig. 1: molybdenum-based oxide (ZnMnMo) 3 O 8 ) The elements in the catalyst are uniformly distributed, so that the subsequent uniform chemical reaction is facilitated.
2) The molybdenum-based oxide (ZnMnMo) 3 O 8 ) The X-ray diffraction (XRD) pattern of (i.e., using a Bruker D8 ADVANCE powder crystal diffractometer, cukα as the light source) is shown in fig. 2.
As can be seen from fig. 2: the present example truly synthesizes purer phase ZnMnMo by sol-gel method 3 O 8 Which belongs to a hexagonal system, and the unit cell parameters are as follows:α＝β＝90°，γ＝120°。
3) The molybdenum-based oxide (ZnMnMo) 3 O 8 ) As an active material and a zinc sulfate aqueous solution as an electrolyte, an aqueous zinc ion battery was assembled, and a charge-discharge test (30 cycles of charge-discharge) was performed by a constant current charge-discharge method under conditions of a charge-discharge current density of 100mA/g and a charge-discharge voltage of 0.05V to 1.80V, and the charge-discharge curve was as shown in fig. 3.
As can be seen from fig. 3: the molybdenum-based oxide (ZnMnMo) 3 O 8 ) The discharge capacity of the first ring of the assembled water-based zinc ion battery reaches 242.9mAh/g.
4) The molybdenum-based oxide (ZnMnMo) 3 O 8 ) As active material and zinc sulfate aqueous solution as electrolyte, assembling water-based zinc ion battery, and charging and discharging by constant current methodThe cycle performance test (190 cycles of charge and discharge) was conducted under the conditions of a charge and discharge current density of 100mA/g and a charge and discharge voltage of 0.05V to 1.80V, and the results of the cycle performance test were shown in FIG. 4.
As can be seen from fig. 4: the molybdenum-based oxide (ZnMnMo) 3 O 8 ) The capacity retention rate of the assembled water-based zinc ion battery after 190 times of circulation reaches 73.8 percent.
Example 2:
a molybdenum-based oxide, which is prepared by the following steps:
1) ZnCO 3 ·7H 2 O、MnCO 3 ·H 2 O and Mo 7 N 6 H 24 O 24 ·4H 2 O is added into deionized water according to the mole ratio of Zn, mn and Mo of 1:1:3, stirred for 30min at the constant temperature of 90 ℃, and then mixed according to Mo 7 N 6 H 24 O 24 ·4H 2 Adding citric acid monohydrate into the mixture according to the molar ratio of O to citric acid monohydrate of 1:6 to prepare sol, and continuously stirring until deionized water is evaporated to dryness to obtain wet gel;
2) Adding the wet gel obtained in the step 1) into an oven to bake for 5 hours at 150 ℃ to prepare xerogel, grinding into powder, presintering for 4 hours in argon atmosphere at the temperature of 350 ℃, naturally cooling, and grinding to obtain a presintering product;
3) Grinding the presintered product obtained in the step 2) again and then placing the ground presintered product in H 2 Ar Mixed atmosphere (H) 2 Is sintered for 10 hours at 700 ℃ in the volume fraction of 5 percent) and then naturally cooled to obtain molybdenum-based oxide (ZnMnMo) 3 O 8 )。
Performance test:
1) Through testing (the testing method is the same as that of example 1), the molybdenum-based oxide (ZnMnMo) 3 O 8 ) The elements in the catalyst are uniformly distributed, so that the subsequent uniform chemical reaction is facilitated.
2) The molybdenum-based oxide (ZnMnMo) 3 O 8 ) The X-ray diffraction (XRD, test using Bruker D8 ADVANCE powder crystal diffractometer, cukα as light source) pattern is shown in fig. 5.
As can be seen from fig. 5:the present example truly synthesizes purer phase ZnMnMo by sol-gel method 3 O 8 Which belongs to a hexagonal system, and the unit cell parameters are as follows:α＝β＝90°，γ＝120°。
3) The molybdenum-based oxide (ZnMnMo) 3 O 8 ) As an active material and a zinc sulfate aqueous solution as an electrolyte, an aqueous zinc ion battery was assembled, and a charge-discharge test (30 cycles of charge-discharge) was performed by a constant current charge-discharge method under conditions of a charge-discharge current density of 100mA/g and a charge-discharge voltage of 0.05V to 1.80V, and the charge-discharge curve was as shown in fig. 6.
As can be seen from fig. 6: the molybdenum-based oxide (ZnMnMo) 3 O 8 ) The discharge capacity of the first ring of the assembled water-based zinc ion battery reaches 177.2mAh/g.
Example 3:
a molybdenum-based oxide, which is prepared by the following steps:
1) Zn (CH) 3 COO) 2 ·2H 2 O、Mn(CH 3 COO) 2 ·4H 2 O and MoO 3 Adding the mixture into deionized water according to the mol ratio of Zn, mn and Mo of 1:1:3, stirring at a constant temperature of 90 ℃ for 30min, and then according to MoO 3 Adding citric acid monohydrate into the mixture according to the molar ratio of the citric acid monohydrate of 1:7 to prepare sol, and continuously stirring until deionized water is evaporated to dryness to obtain wet gel;
2) Adding the wet gel obtained in the step 1) into an oven to bake for 5 hours at 150 ℃ to prepare xerogel, grinding into powder, presintering for 4 hours in argon atmosphere at the temperature of 350 ℃, naturally cooling, and grinding to obtain a presintering product;
3) Grinding the presintered product obtained in the step 2) again and then placing the ground presintered product in H 2 Ar Mixed atmosphere (H) 2 Is sintered for 10 hours at 800 ℃ in the volume fraction of 5 percent) and then naturally cooled to obtain molybdenum-based oxide (ZnMnMo) 3 O 8 )。
Performance test:
1) Through testing (measuring)The test method is the same as in example 1), the molybdenum-based oxide (ZnMnMo) 3 O 8 ) The elements in the catalyst are uniformly distributed, so that the subsequent uniform chemical reaction is facilitated.
2) The molybdenum-based oxide (ZnMnMo) 3 O 8 ) The X-ray diffraction (XRD) pattern of (i.e., using a Bruker D8 ADVANCE powder crystal diffractometer, with cukα as the light source) is shown in fig. 7.
As can be seen from fig. 7: the present example truly synthesizes purer phase ZnMnMo by sol-gel method 3 O 8 Which belongs to a hexagonal system, and the unit cell parameters are as follows:α＝β＝90°，γ＝120°。
3) The molybdenum-based oxide (ZnMnMo) 3 O 8 ) As an active material and a zinc sulfate aqueous solution as an electrolyte, an aqueous zinc ion battery was assembled, and a charge-discharge test (30 cycles of charge-discharge) was performed by a constant current charge-discharge method under conditions of a charge-discharge current density of 100mA/g and a charge-discharge voltage of 0.05V to 1.70V, and the charge-discharge curve obtained was shown in fig. 8.
As can be seen from fig. 8: the molybdenum-based oxide (ZnMnMo) 3 O 8 ) The discharge capacity of the first ring of the assembled water-based zinc ion battery reaches 68.0mAh/g.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (10)
1. A molybdenum-based oxide is characterized in that the chemical formula is ZnMnMo 3 O 8 Belongs to a hexagonal system, and has unit cell parameters ofα＝β＝90°，γ＝120°。
2. A method for producing the molybdenum-based oxide as defined in claim 1, comprising the steps of:
1) Dispersing a zinc source, a manganese source, a molybdenum source and an organic chelating agent in water to prepare sol, and heating to evaporate water to obtain wet gel;
2) Drying the wet gel obtained in the step 1) to obtain xerogel, and presintering to obtain a presintering product;
3) And (3) placing the presintered product in the step (2) in a reducing atmosphere for sintering to obtain the molybdenum-based oxide.
3. The preparation method according to claim 2, characterized in that: step 1) the zinc is at least one of zinc acetate, zinc carbonate and zinc nitrate; the manganese source in the step 1) is at least one of manganese acetate, manganese carbonate, manganese acetylacetonate, manganese dioxide, manganese monoxide and manganese sesquioxide; the molybdenum source in the step 1) is at least one of ammonium molybdate, molybdenum acetylacetonate, molybdic acid, molybdenum trioxide and molybdenum dioxide; the organic chelating agent in the step 1) is at least one of citric acid, ascorbic acid and oxalic acid.
4. A method of preparation according to claim 2 or 3, characterized in that: step 1) adding a zinc source, a manganese source and a molybdenum source according to a mole ratio of Zn, mn and Mo of 1:1:3; the molar ratio of the molybdenum source to the organic chelating agent in the step 1) is 1:4-9.
5. A method of preparation according to claim 2 or 3, characterized in that: the water evaporation in the step 1) is carried out under the condition that the temperature is 60-100 ℃; the drying in the step 2) is carried out at the temperature of 70-150 ℃.
6. The preparation method according to claim 2, characterized in that: and 2) presintering at 200-400 ℃ for 3-6 h.
7. The preparation method according to claim 2, characterized in that: the sintering in the step 3) is carried out at 600-800 ℃ for 8-12 h.
8. The production method according to any one of claims 2, 3, 6 and 7, characterized in that: the presintering in the step 2) is carried out in an air atmosphere, a reducing atmosphere or a protective atmosphere; step 3) the reducing atmosphere is Ar-H 2 Mixed atmosphere, N 2 -H 2 A mixed atmosphere, a hydrogen atmosphere and an ammonia atmosphere.
9. A negative electrode material comprising the molybdenum-based oxide according to claim 1.
10. An aqueous zinc ion battery comprising the negative electrode material according to claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311508463.4A CN117650231A (en) | 2023-11-13 | 2023-11-13 | Molybdenum-based oxide, preparation method thereof, anode material and water-based zinc ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311508463.4A CN117650231A (en) | 2023-11-13 | 2023-11-13 | Molybdenum-based oxide, preparation method thereof, anode material and water-based zinc ion battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117650231A true CN117650231A (en) | 2024-03-05 |
Family
ID=90046989
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311508463.4A Pending CN117650231A (en) | 2023-11-13 | 2023-11-13 | Molybdenum-based oxide, preparation method thereof, anode material and water-based zinc ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117650231A (en) |
-
2023
- 2023-11-13 CN CN202311508463.4A patent/CN117650231A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108598390B (en) | Preparation method of positive electrode material for lithium-sulfur battery and lithium-sulfur battery | |
| CN111082058B (en) | Nasicon structure sodium titanium phosphate surface modified P2 type manganese-based sodium ion battery positive electrode material and preparation method thereof | |
| CN111564622A (en) | Lithium manganese iron phosphate cathode material and preparation method thereof | |
| CN112885985B (en) | Positive pole piece and preparation method thereof, electrochemical energy storage device and pre-metallization method of electrochemical energy storage device | |
| CN114709391B (en) | Positive electrode lithium supplementing material, preparation method thereof and lithium ion battery | |
| CN107093739B (en) | Potassium manganese oxide for potassium ion battery anode material and preparation method thereof | |
| CN111244561B (en) | Preparation method of high-energy-density and high-voltage graphite-zinc-based ion battery based on aqueous electrolyte | |
| CN111769272A (en) | Bi @ C hollow nanosphere composite material and preparation method and application thereof | |
| CN112701260B (en) | In-situ carbon-coated titanium niobate composite material and preparation method and application thereof | |
| CN112599765A (en) | Sodium/potassium-doped high-performance lithium-manganese-nickel-based positive electrode material and preparation method thereof | |
| CN111584840A (en) | Carbon cloth loaded carbon-coated nickel disulfide nanosheet composite material and preparation method and application thereof | |
| CN110752360B (en) | S-Ni3Preparation method of C/NiO composite lithium-sulfur battery positive electrode material | |
| CN115133023A (en) | Preparation method of doped modified ferric sodium pyrophosphate cathode material | |
| CN114906884A (en) | Preparation method of fluorine-niobium double-doped lithium niobate-coated ternary material | |
| CN106920952B (en) | A kind of preparation method of modified nickel lithium manganate cathode material | |
| CN113363460A (en) | Preparation method of lithium ion battery negative electrode material zinc nickelate bimetallic oxide | |
| WO2023093180A1 (en) | Nickel-rich high-voltage sodium-ion positive electrode material for battery, preparation method therefor, and application thereof | |
| CN110931750A (en) | Copper-doped cobalt oxide porous nanosheet composite material and energy storage application | |
| CN111446454B (en) | Application of electronic compound as lithium air battery anode catalyst material | |
| CN114843459A (en) | Antimony pentasulfide-based material and preparation method and application thereof | |
| CN117650231A (en) | Molybdenum-based oxide, preparation method thereof, anode material and water-based zinc ion battery | |
| CN108400319B (en) | Preparation method of nano-structure cobalt molybdate electrode material | |
| CN112390284A (en) | Preparation method of tin oxide modified cobalt-zinc bimetallic organic framework derived carbon composite material | |
| CN116230873B (en) | Sodium-hydrogen alkaline secondary battery, positive electrode and negative electrode catalyst | |
| CN113130903B (en) | Aluminum oxide coated iron cyanamide material prepared by sol-gel method and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |