CN117509733B - ZnMoO3/C microsphere with intrinsic Zn defect core-shell structure and preparation method and application thereof - Google Patents
ZnMoO3/C microsphere with intrinsic Zn defect core-shell structure and preparation method and application thereof Download PDFInfo
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- 239000011258 core-shell material Substances 0.000 title claims abstract description 75
- 230000007547 defect Effects 0.000 title claims abstract description 62
- 239000004005 microsphere Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000011701 zinc Substances 0.000 claims abstract description 70
- 239000002243 precursor Substances 0.000 claims abstract description 48
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 39
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 33
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003960 organic solvent Substances 0.000 claims abstract description 20
- 238000005245 sintering Methods 0.000 claims abstract description 17
- 150000003751 zinc Chemical class 0.000 claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 150000002751 molybdenum Chemical class 0.000 claims abstract description 11
- 229910052786 argon Inorganic materials 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 238000004729 solvothermal method Methods 0.000 claims abstract description 9
- 102000020897 Formins Human genes 0.000 claims description 15
- 108091022623 Formins Proteins 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 230000002950 deficient Effects 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 claims description 8
- 239000007773 negative electrode material Substances 0.000 claims description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 235000016768 molybdenum Nutrition 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- 239000011684 sodium molybdate Substances 0.000 claims description 5
- 235000015393 sodium molybdate Nutrition 0.000 claims description 5
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 5
- 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 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 4
- 239000011609 ammonium molybdate Substances 0.000 claims description 4
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 4
- 229940010552 ammonium molybdate Drugs 0.000 claims description 4
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 2
- 229940102001 zinc bromide Drugs 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 15
- 229910052799 carbon Inorganic materials 0.000 abstract description 15
- 238000009792 diffusion process Methods 0.000 abstract description 4
- 239000010406 cathode material Substances 0.000 abstract description 3
- 238000012983 electrochemical energy storage Methods 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- IHCCLXNEEPMSIO-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 IHCCLXNEEPMSIO-UHFFFAOYSA-N 0.000 description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 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 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000002131 composite material Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 238000001027 hydrothermal synthesis Methods 0.000 description 7
- 230000000630 rising effect Effects 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 230000001351 cycling effect Effects 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 239000012046 mixed solvent Substances 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000001132 ultrasonic dispersion Methods 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
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- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 description 3
- 238000004435 EPR spectroscopy Methods 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- ZQCQTPBVJCWETB-UHFFFAOYSA-N 4-fluoro-1,3-dioxol-2-one Chemical compound FC1=COC(=O)O1 ZQCQTPBVJCWETB-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000010485 coping Effects 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000002149 hierarchical pore Substances 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
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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
Abstract
The invention relates to the technical field of electrochemical energy storage, in particular to an intrinsic Zn defect core-shell structure ZnMoO 3 A/C microsphere and its preparation method and application are provided. The preparation method comprises the following steps: dispersing zinc salt and molybdenum salt in a mixed organic solvent, and performing solvothermal reaction to obtain a precursor A; sintering the precursor A to obtain a precursor B; calcining the precursor B in a mixed atmosphere to obtain the ZnMoO with the intrinsic Zn defect core-shell structure 3 microspheres/C; the mixed atmosphere is a mixed atmosphere of hydrogen and argon. The method is simple, efficient and high in repeatability, and no additional carbon source is needed. The ZnMoO of the invention 3 The existence of the/C intrinsic Zn defect effectively improves the storage capacity of sodium ions on the surface of the electrode and accelerates the diffusion kinetics of the sodium ions. ZnMoO prepared by the method of the invention 3 and/C shows high specific capacity, long cycle life and excellent rate performance in the sodium ion battery cathode material.
Description
Technical Field
The invention relates to the technical field of electrochemical energy storage, in particular to an intrinsic Zn defect core-shell structure ZnMoO 3 A/C microsphere and its preparation method and application are provided.
Background
In response to the call for carbon neutralization, a key challenge to overcome is to find an advanced electrochemical energy storage device with high energy density, environmental protection and high safety, which is suitable for large-scale energy storage and rapid charge and discharge. Lithium ion batteries are widely used in the fields of portable electronic products, new energy electric automobiles and the like due to high energy density and good cycling stability. However, the increasing demand for lithium ion batteries is not matched to the scarcity and uneven distribution of lithium resources on earth, and therefore a viable alternative needs to be found. Because sodium resources are abundant and low in price, and the lithium intercalation property is similar to that of lithium, the 'rocking chair' battery theoretical model applicable to lithium ion batteries is also applicable to sodium ion batteries, so that the sodium ion batteries are considered to be the most likely to replace the lithium ion batteries for large-scale energy storage systems.
The cathode material is used as an important component of the sodium ion battery and is a key ring for realizing the sodium ion battery with high energy density. However, graphite negative electrodes suitable for lithium ion batteries are not suitable for sodium ion batteries due to the potential safety hazards caused by limited capacity and the tendency to cause sodium dendrite growth; the alloy material has higher theoretical specific capacity, but volume expansion can occur in the charge and discharge process, so that the electrode material is pulverized, and the cycle life is short; the organic negative electrode material has the defects of easy dissolution in electrolyte, poor electronic conductivity, relatively low energy density and the like. Therefore, it is urgent to find a novel low-cost anode material with high specific capacity and good cycle stability.
Transition metal oxide based on a conversion reaction mechanism has the characteristics of high theoretical specific capacity, wide sources and strong safety, and becomes an attractive cathode candidate material. Among them, molybdenum-based materials in transition metal oxides have abundant physicochemical properties, controllable valence states and a layered structure that facilitates intercalation of sodium ions, and are widely considered as one of the most promising negative electrode materials for sodium ion batteries. Meanwhile, the bi-metal oxide shows better electrochemical performance than the mono-metal oxide because it can provide a richer redox reaction and benefit from the synergistic effect of a plurality of metal active sites. For example, a bimetallic oxide ZnMoO based on cost advantages (abundant zinc, molybdenum reserves) and multiple electron transfer advantages 4 Shows remarkable electrochemical performance and becomes a new kind of oxide-based negative electrode of lithium ion batteries and sodium ion batteries. However, such transition metal oxide electrodes have inherent poor electron conductivity, retarded ionic conduction, and solid electrolyte interface (SEI) The membrane is unstable and is easy to generate chalking in the conversion process, thereby causing the problems of short cycle life, poor rate performance and the like. These problems seriously hamper the practical application of the materials in the field of sodium ion batteries. Therefore, in the prior art, development of a novel material with long cycle life, high specific capacity, excellent rate performance and other excellent electrochemical properties and simple preparation method is needed to meet the energy storage development requirement of sodium ion batteries.
Disclosure of Invention
Based on the above, the present invention provides an intrinsic Zn defect core-shell structure ZnMoO 3 A/C microsphere and its preparation method and application are provided. ZnMoO 3 The core-shell porous structure of/C is not only beneficial to effective exposure of an active interface and infiltration of electrolyte, but also establishes a good electron/ion transmission high-speed channel in cooperation with a carbon layer, thereby promoting rapid and stable sodium storage. In addition, the existence of intrinsic Zn defects effectively improves the storage capacity of sodium ions on the surface of the electrode, and further accelerates diffusion kinetics. ZnMoO 3 The core-shell framework structure and the defect engineering of the/C are cooperated to accelerate the cycle stability and the rate capability of the sodium ion battery.
In order to achieve the above object, the present invention provides the following solutions:
according to one of the technical schemes of the invention, an intrinsic Zn defect core-shell structure ZnMoO 3 The preparation method of the/C microsphere comprises the following steps:
dispersing zinc salt and molybdenum salt in a mixed organic solvent, and performing solvothermal reaction to obtain a precursor A;
sintering the precursor A to obtain a precursor B;
calcining the precursor B in a mixed atmosphere to obtain the ZnMoO with the intrinsic Zn defect core-shell structure 3 microspheres/C;
the mixed atmosphere is a mixed atmosphere of hydrogen and argon.
According to the second technical scheme of the invention, the ZnMoO with the intrinsic Zn defect core-shell structure is prepared by the preparation method 3 and/C microspheres.
In a third aspect of the present invention, the above-mentioned intrinsic Zn-deficient core-shell junctionStructural ZnMoO 3 Use of/C microspheres in sodium ion batteries.
According to the fourth technical scheme, the negative electrode material of the sodium ion battery comprises the intrinsic Zn defect core-shell structure ZnMoO 3 and/C microspheres.
The fifth technical scheme of the invention is that the sodium ion battery comprises the sodium ion battery anode material.
The invention discloses the following technical effects:
the method is simple, efficient and high in repeatability, and no additional carbon source is needed.
The method of the invention utilizes a unique porous core-shell structure to establish an extremely stable framework, so that ZnMoO 3 Exposing rich active interface to raise capacity, shorten sodium ion diffusion path and speed reaction kinetics. In addition, znMoO 3 The core-shell structure of/C provides sufficient volume buffer space, which is beneficial to stable sodium storage behavior.
The ZnMoO of the invention 3 The existence of intrinsic Zn defects in the/C effectively improves the storage capacity of sodium ions on the surface of the electrode and accelerates the diffusion kinetics of the sodium ions. ZnMoO prepared by the method of the invention 3 and/C shows high specific capacity, long cycle life and excellent rate performance in the sodium ion battery cathode material.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a ZnMoO of an intrinsic Zn defect core-shell structure prepared in example 4 of the invention 3 X-ray diffraction pattern of/C microspheres;
FIG. 2 is a ZnMoO of intrinsic Zn defect core-shell structure prepared in example 4 of the invention 3 C field emission scanning electron micrographs of the microspheres;
FIG. 3 shows the present inventionZnMoO with intrinsic Zn defect core-shell structure prepared in example 4 3 Field emission transmission electron micrographs of the/C microspheres;
FIG. 4 shows an intrinsic Zn defect core-shell structure ZnMoO prepared in example 4 of the invention 3 Field emission high resolution transmission electron micrographs of/C microspheres; wherein, (a) is a high resolution transmission electron micrograph of 5 nm grade and (b) is a high resolution transmission electron micrograph of 1 nm grade;
FIG. 5 shows an intrinsic Zn defect core-shell structure ZnMoO prepared in example 4 of the invention 3 Nitrogen adsorption-desorption curve and pore size distribution map of the microspheres; wherein, (a) is a nitrogen adsorption-desorption curve, and (b) is a pore size distribution map;
FIG. 6 shows an intrinsic Zn defect core-shell structure ZnMoO of the invention prepared in example 4 3 Electron paramagnetic resonance curve of the/C microsphere;
FIG. 7 shows an intrinsic Zn defect core-shell structure ZnMoO of the invention prepared in example 4 3 microspheres/C at 0.1A g -1 Cycling performance plot at current density;
FIG. 8 shows an intrinsic Zn defect core-shell structure ZnMoO of the invention prepared in example 4 3 microspheres/C1.0A g -1 Cycling performance plot at current density;
FIG. 9 is a ZnMoO of an intrinsic Zn defect core-shell structure prepared in example 4 of the invention 3 Graph of the rate performance of the/C microspheres at different current densities.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples of the present invention are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
As used herein, the term "room temperature", unless otherwise indicated, means 15 to 30 ℃.
The first aspect of the invention provides an intrinsic Zn defect core-shell structure ZnMoO 3 The preparation method of the/C microsphere comprises the following steps:
dispersing zinc salt and molybdenum salt in a mixed organic solvent, and performing solvothermal reaction to obtain a precursor A (Zn-Mo precursor solid spheres doped with the organic solvent);
sintering the precursor A to obtain a precursor B (core-shell structure Zn-Mo oxide doped with an organic solvent, namely core-shell structure ZnMoO) x ）；
Calcining the precursor B in a mixed atmosphere to obtain the ZnMoO with the intrinsic Zn defect core-shell structure 3 microspheres/C;
the mixed atmosphere is a mixed atmosphere of hydrogen and argon.
The invention also tries to replace zinc salt by nickel salt, copper salt and other metal salts, and the result shows that the prepared product contains impurities and cannot obtain pure-phase product. Notably, the formation of the core-shell structure is due to the kinetic differences of the thermal motion of the different metallic elements during the high temperature sintering process.
In a preferred embodiment of the present invention, the zinc salt is at least one of zinc nitrate, zinc sulfate, zinc acetate, zinc chloride, zinc fluoride and zinc bromide; the molybdenum salt is at least one of sodium molybdate, ammonium molybdate and molybdenum acetylacetonate;
the mixed organic solvent is at least two of methanol, ethanol, isopropanol, acetone, dimethylformamide, acetonitrile and glycerol; further preferably, the mixed solvent is two of methanol, ethanol, isopropanol, acetone, dimethylformamide, acetonitrile and glycerin, and the volume ratio of the two solvents is (10-20) (60-78).
A single organic solvent cannot obtain a material of a spherical structure, and three or more organic solvents affect the purity of the final product, so that the present invention is preferably limited to two organic solvents.
The ratio of the two organic solvents will determine the carbon content of the final product, and a suitable amount of carbon content will result in a material with high capacity and good stability. If the carbon content is low, a material with good cycle performance cannot be obtained; while too high a carbon content results in less active material and ultimately in low capacity. The ratio of the two organic solvents is beyond the range described above, so that products with different carbon contents can be obtained, and finally the sodium storage performance is affected.
The ZnMoO with the intrinsic Zn defect core-shell structure 3 The carbon in the/C microsphere is derived from an organic solvent, so that the step of additionally carrying out carbon coating is omitted, and the raw materials and the preparation flow are saved.
The molar ratio of the zinc salt to the molybdenum salt is 1:1; the concentration of the zinc salt in the mixed organic solvent is 3-15 mmol/L.
In a preferred embodiment of the invention, the solvothermal reaction is carried out at a temperature of 120-180 ℃ for 6-12 hours.
In a preferred embodiment of the present invention, the solvothermal reaction further comprises a step of sequentially rinsing with absolute ethanol and deionized water and drying.
In a preferred embodiment of the present invention, the step of dispersing the zinc salt and the molybdenum salt in the mixed organic solvent for solvothermal reaction to obtain the precursor a includes dispersing the zinc salt and the molybdenum salt in the mixed organic solvent, magnetically stirring for 5-50 min, and ultrasonically stirring for 10-100 min (the purpose of the magnetic stirring and the ultrasonic stirring is to fully dissolve the zinc salt and the molybdenum salt in the mixed organic solvent), and performing solvothermal reaction to obtain the precursor a (zn—mo precursor solid spheres doped with the organic solvent).
In a preferred embodiment of the present invention, the sintering is specifically performed in an air atmosphere at 2 to 8 ℃ for a minute -1 The temperature is raised to 300-500 ℃ and the temperature is kept for 0.5-5.0 h.
The purpose of sintering is to form Zn-Mo oxides of the core-shell structure. During sintering, the formation of a shell-core structure is caused by the inconsistent dynamics of the thermal motion of different metal elements; when the sintering temperature is too low, a core-shell structure cannot be formed, and when the sintering temperature is too high, collapse of the core-shell structure is caused. Therefore, the sintering temperature is preferably limited to 300-500 ℃.
The reason why the sintering time is limited to the above range is that: during sintering, the formation of a shell-core structure is caused by the inconsistent dynamics of the thermal motion of different metal elements; when the sintering time is too short, a shell-core structure cannot be formed, and when the sintering time is too long, collapse of the shell-core structure can be caused. Therefore, the sintering time is preferably limited to 0.5-5.0 h.
In the preferred embodiment of the invention, the volume ratio of the hydrogen to the argon in the mixed atmosphere is (0-10): (90-100).
The reason for adopting the mixed atmosphere of hydrogen and argon is as follows: a proper amount of reducing atmosphere can obtain pure-phase ZnMoO 3 and/C. Importantly, proper reducing atmosphere is a key factor for obtaining intrinsic Zn defects, because materials with intrinsic Zn defects cannot be obtained when the hydrogen ratio is small, and pure-phase ZnMoO cannot be obtained when the hydrogen ratio is high 3 C; therefore, the volume ratio of hydrogen to argon in the mixed atmosphere is preferably limited to be (0-10) (90-100).
In a preferred embodiment of the present invention, the calcination is specifically performed at 2 to 8 ℃ for a minute -1 The temperature is raised to 400-700 ℃ for heat preservation for 1-10 h.
The carbonization (calcination) step in the composite atmosphere of argon and hydrogen is the key for carbonizing organic matters to obtain carbon, and the calcination step obtains proper amount of ZnMoO coated with carbon 3 . The calcination temperature is low, the carbonization of the organic matters is incomplete, and the lower coulomb efficiency is caused; and the calcination temperature is too high, so that ZnMoO is damaged 3 The core-shell structure of/C, in turn, results in poor cycling performance.
The second aspect of the invention provides an intrinsic Zn defect core-shell structure ZnMoO prepared by the preparation method 3 and/C microspheres.
The third aspect of the invention provides the ZnMoO with the intrinsic Zn defect core-shell structure 3 Use of/C microspheres in sodium ion batteries.
The fourth aspect of the invention provides a negative electrode material of a sodium ion battery, which comprises the intrinsic Zn defect core-shell structure ZnMoO 3 and/C microspheres.
The fifth aspect of the invention provides a sodium ion battery, comprising the sodium ion battery anode material.
The raw materials used in the examples of the present invention, unless otherwise specified, were all available commercially.
In the invention, the ZnMoO with the intrinsic Zn defect core-shell structure 3 The method for performing performance test by using the/C microsphere as the negative electrode to assemble the sodium ion battery comprises the following specific steps: the CR2032 type coin cell was assembled in an argon-filled glove box. The working electrode is made of ZnMoO as active material 3 C (70 wt%), conductive carbon (provider P,20 wt%), polyvinylidene fluoride (PVDF, 10%) were mixed in N-methylpyrrolidone (NMP), finally uniformly coated on copper foil, and dried under vacuum at 70 ℃. Each ZnMoO 3 The active material mass loading of the/C pole piece (working electrode) was about 1.2 mg/cm 2 . In assembling the sodium-ion half-cell, znMoO 3 And the C electrode, the metallic sodium and the glass fiber are respectively used as a working electrode, a counter electrode and a diaphragm. The electrolyte adopts 1M sodium perchlorate (NaClO) 4 ) Dissolved in Ethylene Carbonate (EC)/Propylene Carbonate (PC) (1:1, volume ratio)/fluoroethylene carbonate (FEC, 5.0. 5.0 wt%).
The invention is described in detail below with reference to the drawings and the specific embodiments, but the invention is not limited thereto.
Example 1
Step 1, dispersing 0.3 mmol of zinc nitrate and 0.3 mmol of sodium molybdate into a mixed solvent of 10 mL methanol and 60 mL acetone, stirring for 5 min at room temperature, and performing ultrasonic dispersion for 10 min to completely dissolve.
And 2, placing the solution into a high-pressure hydrothermal reaction kettle, and preserving heat at 120 ℃ for 6 h to realize full reaction. After the reaction is finished, sequentially rinsing with absolute ethyl alcohol and deionized water, and drying at 80 ℃ to obtain a precursor A.
Step 3, placing the precursor A in a muffle furnace at 2 ℃ for min -1 And raising the temperature to 300 ℃ and preserving heat by 0.5 h to obtain a precursor B.
Step 4, putting the precursor B obtained in the step 3 into a reactor which is filled with H 2 In a tube furnace of Ar (volume ratio 1:100) composite gas, the temperature is 2 ℃ for min -1 Heating to 400 ℃ at a temperature rising rate, preserving heat for 1 h, and naturally cooling to obtain the ZnMoO with the intrinsic Zn defect core-shell structure 3 and/C microspheres.
ZnMoO with intrinsic Zn defect core-shell structure prepared in the embodiment 3 The performance test of the sodium ion battery assembled by taking the/C microsphere as the negative electrode shows that the intrinsic Zn defect core-shell structure ZnMoO prepared in the embodiment 3 microspheres/C at 0.1A g -1 The specific charge capacity after 200 times of charge and discharge under the current density is 69.2 mAh g -1 The method comprises the steps of carrying out a first treatment on the surface of the At 1.0A g -1 The specific charge capacity after 1000 times of charge and discharge under the current density is 48.6 mAh g -1 The method comprises the steps of carrying out a first treatment on the surface of the At 20.0A g -1 The specific charge capacity at high rate is 33.3 mAh g -1 。
Example 2
Step 1, dispersing 0.5 mmol of zinc sulfate and 0.5 mmol of ammonium molybdate into a mixed solvent of 11 mL ethanol and 65 mL dimethylformamide, stirring for 10 min at room temperature, and performing ultrasonic dispersion for 20 min to completely dissolve.
And 2, placing the solution into a high-pressure hydrothermal reaction kettle, and preserving heat at 130 ℃ for 7 h to realize full reaction. After the reaction is finished, sequentially rinsing with absolute ethyl alcohol and deionized water, and drying at 80 ℃ to obtain a precursor A.
Step 3, placing the precursor A in a muffle furnace at 3 ℃ for min -1 And raising the temperature to 330 ℃ and preserving heat for 1 h to obtain a precursor B.
Step 4, putting the precursor B into a reactor which is communicated with H 2 In a tube furnace of Ar (volume ratio 2:100) composite gas, 3 ℃ for min -1 Heating to 450 ℃ at a temperature rising rate, preserving heat by 1.5. 1.5 h, and naturally cooling to obtain the ZnMoO with the intrinsic Zn defect core-shell structure 3 and/C microspheres.
ZnMoO with intrinsic Zn defect core-shell structure prepared in the embodiment 3 The performance test of the sodium ion battery assembled by taking the/C microsphere as the negative electrode shows that the intrinsic Zn defect core-shell structure ZnMoO prepared in the embodiment 3 microspheres/C at 0.1A g -1 The specific charge capacity after 200 times of charge and discharge under the current density is 125.9 mAh g -1 The method comprises the steps of carrying out a first treatment on the surface of the At 1.0A g -1 The specific charge capacity after 1000 times of charge and discharge under the current density is 65.5 mAh g -1 The method comprises the steps of carrying out a first treatment on the surface of the At 20.0A g -1 The specific charge capacity at high rate is 40.5 mAh g -1 。
Example 3
Step 1, dispersing 0.6 mmol of zinc acetate and 0.6 mmol of molybdenum acetylacetonate into a mixed solvent of 13 mL isopropanol and 66 mL acetonitrile, stirring for 15 min at room temperature, and performing ultrasonic dispersion for 30 min to completely dissolve.
And 2, placing the solution into a high-pressure hydrothermal reaction kettle, and preserving heat at 140 ℃ for 8 h to realize full reaction. After the reaction is finished, sequentially rinsing with absolute ethyl alcohol and deionized water, and drying at 80 ℃ to obtain a precursor A.
Step 3, placing the precursor A in a muffle furnace at 4 ℃ for min -1 And raising the temperature to 350 ℃ and preserving heat for 2 h to obtain a precursor B.
Step 4, the precursor is processedB put in and let in H 2 In a tube furnace of Ar (volume ratio 3:100) composite gas, the temperature is 4 ℃ for min -1 Heating to 500 ℃ at a temperature rising rate, preserving heat for 2 h, and naturally cooling to obtain the ZnMoO with the intrinsic Zn defect core-shell structure 3 and/C microspheres.
ZnMoO with intrinsic Zn defect core-shell structure prepared in the embodiment 3 The performance test of the sodium ion battery assembled by taking the/C microsphere as the negative electrode shows that the intrinsic Zn defect core-shell structure ZnMoO prepared in the embodiment 3 microspheres/C at 0.1A g -1 The specific charge capacity after 200 times of charge and discharge under the current density is 232.6 mAh g -1 The method comprises the steps of carrying out a first treatment on the surface of the At 1.0A g -1 The specific charge capacity is 165.5 mAh g after 1000 times of charge and discharge under the current density -1 The method comprises the steps of carrying out a first treatment on the surface of the At 20.0A g -1 The specific charge capacity at high rate is 77.0 mAh g -1 。
Example 4
Step 1, dispersing 0.65 mmol of zinc chloride and 0.65 mmol of sodium molybdate into a mixed solvent of 15 mL acetone and 70 mL glycerin, stirring for 20 min at room temperature, and performing ultrasonic dispersion for 40 min to completely dissolve.
And 2, placing the solution into a high-pressure hydrothermal reaction kettle, and preserving heat at 150 ℃ to realize full reaction by 9 and h. After the reaction is finished, sequentially rinsing with absolute ethyl alcohol and deionized water, and drying at 80 ℃ to obtain a precursor A.
Step 3, placing the precursor A in a muffle furnace at 5 ℃ for min -1 And raising the temperature to 400 ℃ and preserving heat for 3 h to obtain a precursor B.
Step 4, putting the precursor B into a reactor which is communicated with H 2 In a tube furnace of Ar (volume ratio 4:100) composite gas, the temperature is 5 ℃ for min -1 Heating to 550 ℃ at a temperature rising rate, preserving heat for 3 h, and naturally cooling to obtain the ZnMoO with the intrinsic Zn defect core-shell structure 3 and/C microspheres.
ZnMoO with intrinsic Zn defect core-shell structure prepared in the embodiment 3 microspheres/C (ZnMoO for short) 3 and/C) characterization was performed as follows (ZnMoO in the following figures) 3 @C represents ZnMoO 3 /C）：
FIG. 1 is a ZnMoO of intrinsic Zn defect core-shell structure prepared in example 4 3 C microXRD pattern of the spheres. Analysis of FIG. 1 shows that the intrinsic Zn defect core-shell structure ZnMoO 3 XRD peak position of/C microsphere and ZnMoO 3 The peaks of the standard PDF card (PDF # 35-0019) were identical in position, proving that the ZnMoO was prepared 3 Cc is a pure phase cubic system ZnMoO 3 No other impurity phase.
FIG. 2 is a ZnMoO of intrinsic Zn defect core-shell structure prepared in example 4 3 Scanning electron microscope image of/C microsphere. As can be seen from FIG. 2, the prepared ZnMoO with intrinsic Zn defect core-shell structure 3 the/C microspheres showed a distinct core-shell structure with an average size of about 500-600 nm.
FIG. 3 is an intrinsic Zn-deficient core-shell structure ZnMoO prepared in example 4 3 Transmission electron microscopy of/C microspheres, as can be seen in fig. 3, znMoO 3 and/C shows a distinct yolk-core-shell structure.
FIG. 4 is a ZnMoO of intrinsic Zn defect core-shell structure prepared in example 4 3 High resolution transmission electron microscopy of/C microspheres ZnMoO with 0.491 nm interplanar spacing was measured from FIG. 4 (a) 3 Is (111) crystal plane of (B), which indicates ZnMoO 3 At the same time, a pronounced atom loss can be observed. Importantly, in FIG. 4 (b), znMoO with 0.30. 0.30 nm interplanar spacing was observed 3 And the crystal lattice exhibits a significant Zn atom deficiency, indicating an intrinsic Zn defect ZnMoO 3 Successful preparation of/C.
FIG. 5 is a ZnMoO of intrinsic Zn defect core-shell structure prepared in example 4 3 Nitrogen adsorption-desorption curve (a) and pore size distribution curve (b) of the/C microspheres, znMoO was found from FIG. 5 (a) 3 Specific surface area of/C. Apprxeq.37.0. 37.0 m 2 g -1 And in fig. 5 (b), a hierarchical pore structure with micropores and mesopores coexisting is presented, which accelerates the infiltration of the electrolyte, provides a rich volume buffer space for coping with the rapid sodium treatment/sodium removal process in the charge and discharge process, and is beneficial to better cycle performance.
FIG. 6 is a ZnMoO of intrinsic Zn defect core-shell structure prepared in example 4 3 Electron paramagnetic resonance curve of/C microspheres. As can be seen from FIG. 6, znMoO 3 The signal of/C is obvious near g=2.004, the evidenceThe existence of Zn vacancy is clear, which further indicates that the ZnMoO with the intrinsic Zn defect core-shell structure is successfully prepared 3 and/C microspheres.
ZnMoO with intrinsic Zn defect core-shell structure prepared in the embodiment 3 The performance test results of the/C microspheres as negative electrode assembled sodium ion battery are shown in FIGS. 7-9. FIG. 7 shows an intrinsic Zn-deficient core-shell structure ZnMoO prepared in this example 3 microspheres/C at 0.1A g -1 Cycling performance plot at current density; as can be seen from FIG. 7, znMoO 3 with/C at 0.1A g -1 The specific charge capacity after 200 times of charge and discharge under the current density is 278.6 mAh g -1 The method comprises the steps of carrying out a first treatment on the surface of the FIG. 8 shows an intrinsic Zn-deficient core-shell structure ZnMoO prepared in this example 3 microspheres/C1.0A g -1 Cycling performance plot at current density; as can be seen from FIG. 8, znMoO 3 C at 1.0A g -1 The specific charge capacity after 3200 circles of charge and discharge under the current density is 176.5 mAh g -1 The method comprises the steps of carrying out a first treatment on the surface of the FIG. 9 shows an intrinsic Zn-deficient core-shell structure ZnMoO prepared in this example 3 A graph of the rate performance of the/C microspheres at different current densities; as can be seen from FIG. 9, znMoO 3 C at 20.0A g -1 The specific charge capacity at high multiplying power is 90.8 mAh g -1 . From FIGS. 7 to 9, it can be seen that the intrinsic Zn-deficient core-shell structure ZnMoO prepared in this example 3 the/C microspheres exhibit excellent long cycle life and rate performance as negative electrode materials for sodium ion batteries.
Example 5
Step 1, 0.7 mmol of zinc fluoride and 0.7 mmol of ammonium molybdate are dispersed into a mixed solvent of 16 mL glycerol and 72 mL methanol, stirred for 30 min at room temperature and dispersed by ultrasound for 50 min until complete dissolution.
And 2, placing the solution into a high-pressure hydrothermal reaction kettle, and preserving heat at 160 ℃ for 10 h to realize full reaction. After the reaction is finished, sequentially rinsing with absolute ethyl alcohol and deionized water, and drying at 80 ℃ to obtain a precursor A.
Step 3, placing the precursor A in a muffle furnace at 6 ℃ for min -1 And raising the temperature to 450 ℃ and preserving heat for 4 h to obtain a precursor B.
Step 4, putting the precursor B into a reactor which is communicated with H 2 Ar (volume)Ratio of 5:100) of composite gas in a tube furnace at 6 ℃ for min -1 Heating to 600 ℃ at a temperature rising rate of 4 h, and naturally cooling to obtain the ZnMoO with the intrinsic Zn defect core-shell structure 3 and/C microspheres.
ZnMoO with intrinsic Zn defect core-shell structure prepared in the embodiment 3 The performance test of the sodium ion battery assembled by taking the/C microsphere as the negative electrode shows that the intrinsic Zn defect core-shell structure ZnMoO prepared in the embodiment 3 microspheres/C at 0.1A g -1 The specific charge capacity after 200 times of charge and discharge under the current density is 160.3 mAh g -1 The method comprises the steps of carrying out a first treatment on the surface of the At 1.0A g -1 The specific charge capacity after 1000 times of charge and discharge under the current density is 127.6 mAh g -1 The method comprises the steps of carrying out a first treatment on the surface of the At 20.0A g -1 The specific charge capacity at high rate is 54.6 mAh g -1 。
Example 6
Step 1, 0.8 mmol of zinc fluoride and 0.8 mmol of molybdenum acetylacetonate were dispersed in 18 mL acetonitrile and 75 mL isopropanol, stirred at room temperature for 40 min and sonicated for 60 min to complete dissolution.
And 2, placing the solution into a high-pressure hydrothermal reaction kettle, and preserving heat at 170 ℃ for 12 h to realize full reaction. After the reaction is finished, sequentially rinsing with absolute ethyl alcohol and deionized water, and drying at 80 ℃ to obtain a precursor A.
Step 3, placing the obtained precursor A in a muffle furnace for 6.5 ℃ min -1 And raising the temperature to 500 ℃ and preserving heat for 5 h to obtain a precursor B.
Step 4, putting the precursor B into a reactor which is communicated with H 2 In a tube furnace of Ar (volume ratio 6:100) compound gas, 6.5 ℃ for min -1 Raising the temperature to 650 ℃ at a temperature rising rate, preserving heat by 5 h, and naturally cooling to obtain the ZnMoO with the intrinsic Zn defect core-shell structure 3 and/C microspheres.
Example 7
Step 1, 0.9 mmol of zinc chloride and 0.9 mmol of sodium molybdate were dispersed into 20 mL ethanol and 78 mL isopropanol, stirred at room temperature for 40 min and sonicated for 60 min to complete dissolution.
And 2, placing the solution into a high-pressure hydrothermal reaction kettle, and preserving heat at 170 ℃ for 12 h to realize full reaction. After the reaction is finished, sequentially rinsing with absolute ethyl alcohol and deionized water, and drying at 80 ℃ to obtain a precursor A.
Step 3, placing the precursor A in a muffle furnace at 8 ℃ for min -1 And raising the temperature to 500 ℃ and preserving heat for 5 h to obtain a precursor B.
Step 4, putting the precursor B into a reactor which is communicated with H 2 In a tube furnace of Ar (volume ratio 7:100) composite gas, 8 ℃ for min -1 Raising the temperature to 650 ℃ at a temperature rising rate, preserving heat by 5 h, and naturally cooling to obtain the ZnMoO with the intrinsic Zn defect core-shell structure 3 and/C microspheres.
The above embodiments are only illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solutions of the present invention should fall within the protection scope defined by the claims of the present invention without departing from the design spirit of the present invention.
Claims (6)
1. ZnMoO with intrinsic Zn defect core-shell structure 3 The preparation method of the/C microsphere is characterized by comprising the following steps:
dispersing zinc salt and molybdenum salt in a mixed organic solvent, and performing solvothermal reaction to obtain a precursor A;
sintering the precursor A to obtain a precursor B;
calcining the precursor B in a mixed atmosphere to obtain the ZnMoO with the intrinsic Zn defect core-shell structure 3 microspheres/C;
the mixed atmosphere is a hydrogen and argon mixed atmosphere;
the zinc salt is at least one of zinc nitrate, zinc sulfate, zinc acetate, zinc chloride, zinc fluoride and zinc bromide; the molybdenum salt is at least one of sodium molybdate, ammonium molybdate and molybdenum acetylacetonate; the mixed organic solvent is methanol and acetone with the volume ratio of (10-20) (60-78); the molar ratio of the zinc salt to the molybdenum salt is 1:1; the concentration of the zinc salt in the mixed organic solvent is 3-15 mmol/L;
the volume ratio of the hydrogen to the argon in the mixed atmosphere is 10 (90-100);
the sintering is specifically carried out in an air atmosphere at 2-8 ℃ for min -1 The temperature is raised to 300-500 ℃ at a rate of 0.5-5.0 h;
the calcination is specifically carried out at 2-8 ℃ for min -1 The temperature is raised to 400-700 ℃ for heat preservation for 1-10 h.
2. The preparation method according to claim 1, wherein the solvothermal reaction is performed at a temperature of 120-180 ℃ for 6-12 hours.
3. The intrinsic Zn-deficient core-shell structure ZnMoO prepared by the preparation method according to claim 1 or 2 3 and/C microspheres.
4. The intrinsic Zn-deficient core-shell structure ZnMoO as set forth in claim 3 3 Use of/C microspheres in sodium ion batteries.
5. A negative electrode material of a sodium ion battery, which is characterized in that the raw material comprises the intrinsic Zn defect core-shell structure ZnMoO of claim 3 3 and/C microspheres.
6. A sodium ion battery comprising the negative electrode material of the sodium ion battery of claim 5.
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