CN114394628A - Carambola-like CoWO with preferred orientation and capacity inverse growth4Microspheres and uses thereof - Google Patents
Carambola-like CoWO with preferred orientation and capacity inverse growth4Microspheres and uses thereof Download PDFInfo
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- CN114394628A CN114394628A CN202210016375.1A CN202210016375A CN114394628A CN 114394628 A CN114394628 A CN 114394628A CN 202210016375 A CN202210016375 A CN 202210016375A CN 114394628 A CN114394628 A CN 114394628A
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- 239000004005 microsphere Substances 0.000 claims abstract description 52
- 239000007772 electrode material Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 16
- 229910019408 CoWO4 Inorganic materials 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000002243 precursor Substances 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 11
- 239000013078 crystal Substances 0.000 claims description 10
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 10
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 6
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- AAQNGTNRWPXMPB-UHFFFAOYSA-N dipotassium;dioxido(dioxo)tungsten Chemical compound [K+].[K+].[O-][W]([O-])(=O)=O AAQNGTNRWPXMPB-UHFFFAOYSA-N 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 9
- 239000002105 nanoparticle Substances 0.000 abstract description 6
- 238000004146 energy storage Methods 0.000 abstract description 5
- 239000011232 storage material Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- OMAWWKIPXLIPDE-UHFFFAOYSA-N (ethyldiselanyl)ethane Chemical compound CC[Se][Se]CC OMAWWKIPXLIPDE-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZXOKVTWPEIAYAB-UHFFFAOYSA-N dioxido(oxo)tungsten Chemical group [O-][W]([O-])=O ZXOKVTWPEIAYAB-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000002057 nanoflower Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- -1 specifically Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/30—Sulfides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2004/32—Spheres
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- 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
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Abstract
The invention discloses carambola-like CoWO with preferred orientation and capacity reverse growth4Microspheres and application thereof, belonging to the technical field of electrode materials. Carambola-like CoWO of the invention4The microscopic morphology of the microspheres is carambola-like microspheres with rough surfaces, specifically, nanoparticles are agglomerated into a round cake-like morphology, and a plurality of round cakes are assembled tangentially to form the carambola-like microspheres, wherein the diameter of each round cake is 0.8-1.6 mu m, and the thickness of each round cake is 100-350 nm; the diameter of the assembled carambola-like microspheres is 1-1.6 mu m, and the carambola-like CoWO of the invention4The microsphere has (002) preferred orientation as an electrode material, has the characteristic of reverse growth of specific capacitance in a circulating process, has excellent electrochemical performance, and is an ideal energy storage material.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to carambola-like CoWO with preferred orientation and capacity-inversion growth4Microspheres and their use.
Background
The shortage of fossil fuels and the harm to the environment and the like compel people to develop green and renewable novel energy storage devices. Among many energy storage devices, super capacitors and lithium ion batteries are widely researched due to the advantages of high power density, high energy density, low preparation cost, environmental friendliness and the like. The electrode material is used as an important component of a super capacitor and a lithium ion battery and becomes a key factor influencing the performance of a device, so that the development of the electrode material with excellent performance, easy rapid synthesis and low cost becomes a research hotspot at present.
Wolframite structure cobalt tungstate (CoWO)4) As an important p-type transition metal oxide, the p-type transition metal oxide has excellent electrochemical activity and more electron multi-valence conductivity, and has attracted attention in the fields of sensors, magnetism, catalysis, electrochemical energy storage batteries and the like. CoWO (cobalt oxide) with remarkable influence on micro-morphology and crystal structure4The performance of electrode materials, researchers at present prepared CoWO with various shapes by solid phase method, coprecipitation, hydrothermal method and other technological methods4Electrode materials such as nanowires, nanoflowers, nanorods, nanoparticles, and the like. However, the synthetic method and the product generally have the problems of complicated preparation process, easy agglomeration of the product, poor uniformity and the like, so that the prepared CoWO4The electrochemical performance of the electrode material is not ideal.
Disclosure of Invention
In view of this, the present application provides a carambola-like CoWO with preferred orientation and volume-retrograde growth4The invention relates to microspheres and application thereof, in particular to carambola-like CoWO prepared by means of a microwave-assisted process4Microspheres, CoWO produced4The microsphere has the advantages of unique microscopic morphology, good crystal structure, easy high-efficiency and rapid synthesis, low cost and the like; the carambola-like CoWO prepared based on the microwave-assisted hydrothermal process4The shape evolution process of the microsphere is CoWO4A nanoparticle nucleation stage, a round cake-shaped morphology stage with a rough surface formed by irregular growth, and a carambola-like micro sphere stage formed by tangent self-assembly of a plurality of round cakes; the shape is formed and the crystal structure with preferred orientation is characterized in that the microwave heating characteristic is utilized, and the temperature is rapidly raised to the reaction temperature (100-140 ℃) under the condition of 700-1000W of power.
The technical scheme of the invention is as follows:
carambola-like CoWO with preferred orientation and capacity inverse growth4The preparation method of the microsphere mainly comprises the following steps:
1) preparing a precursor: placing an aqueous solution containing a cobalt source and tungstate into a microwave hydrothermal reaction kettle, raising the power to 700-1000W for 5-10 min, raising the temperature to 100-140 ℃, reacting for 25-60 min, centrifuging, washing, and drying to obtain a precursor;
2) carambola-like CoWO4Preparing microspheres: sintering the precursor obtained in the step 1) for 1-5 h at 350-450 ℃ in air atmosphere to obtain carambola-like CoWO4And (3) microspheres.
Further, the concentration ratio of cobalt ions to tungstate in the aqueous solution containing a cobalt source and tungstate in step 1) is 1: 1.
further, the concentration of cobalt ions in the step 1) is 1-20 mmol/L.
Further, the aqueous solution containing the cobalt source and the tungstate in the step 1) also contains ammonium fluoride and urea, wherein the concentration of the ammonium fluoride is 5-20mmol/L, and the concentration of the urea is 10-40 mmol/L.
Further, the cobalt source in the step 1) comprises cobalt nitrate, cobalt chloride and cobalt sulfate; the tungstate comprises sodium tungstate and potassium tungstate.
Further, the specific washing process in the step 1) is to use absolute ethyl alcohol and deionized water to respectively wash for 2-5 times.
Further, the drying condition in the step 1) is drying for 2-10 hours at 40-80 ℃ under a vacuum condition.
Further, the temperature rise speed of the sintering in the step 2) is 1-5 ℃/min.
In another aspect, the invention provides carambola-like CoWO with preferred orientation and capacity inverse growth prepared by the method4And (3) microspheres.
Further, the carambola-like CoWO4The microscopic morphology of the microspheres is carambola-like micro-spheres, specifically, nano particles are agglomerated into a round cake-like morphology, and a plurality of round cakes are assembled tangentially to form the carambola-like micro-spheres, wherein the diameter of each round cake is 0.8-1.6 mu m, and the thickness of each round cake is 100-350 nm; the diameter of the assembled carambola-like micron ball is 1-1.6 microns.
Further, the carambola-like CoWO4Crystal structure of microsphere and standard CoWO4(JCPDS card No.72-0479) has a preferred (002) orientation growth tendency.
The invention also provides the carambola-like CoWO4The microspheres are used as electrode materials.
Further, the specific capacitance of the electrode material shows a reverse growth characteristic in a cyclic process, and the initial specific capacity is 147.4F g-1/34.8mA h g-1@10A g-1The capacity remained 161.2% after 7000 cycles.
Further, the electrode material comprises electrode materials of lithium ion batteries and super capacitors.
Compared with the prior art, the invention has the following beneficial effects:
1) the carambola-like CoWO provided by the invention has preferred orientation and capacity inverse growth4The preparation method of the microspheres is obtained through microwave-assisted hydrothermal reaction and subsequent heat treatment, and compared with a common hydrothermal method, the preparation method is simple and convenient to operate, low in cost, short in experimental period (shortened to 1/16-1/5 of other processes), strong in controllability, timely and lower in reaction temperature, free of adjusting the pH value of a precursor, and simultaneously CoWO4The microsphere electrode material has excellent microscopic morphology, good crystal structure, higher purity, better dispersibility and inverse propertyThe circulating capacity is increased, and the electrochemical performance is excellent.
2) CoWO of the invention4The microscopic appearance of the microsphere is a multi-level carambola-like microsphere with a rough surface, specifically, nanoparticles are agglomerated into a round cake-like appearance, a plurality of round cakes are assembled tangentially to form a carambola-like microsphere, and the carambola-like CoWO4Crystal structure of microsphere and standard CoWO4(JCPDS card No.72-0479) has a preferred (002) orientation growth tendency.
3) The carambola-like CoWO of the invention4The specific capacitance of the microsphere as an electrode material shows reverse growth characteristic in the circulation process, and the initial specific capacity is 147.4F g-1/34.8mA h g-1@10A g-1The capacity remained 161.2% after 7000 cycles.
4) The CoWO with the (002) preferred orientation crystal structure4The microsphere material has better conductivity, and CoWO simultaneously4The inverse increase phenomenon of the specific capacity of the microsphere electrode material shows that the microsphere electrode material has excellent structural stability, shows excellent electrochemical performance when used as an electrode material of energy storage devices such as lithium ion batteries and super capacitors, and can meet the commercial application performance index of the energy storage devices.
Drawings
In order to more clearly explain the technical solution in the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below.
FIG. 1 shows CoWO prepared in example 1 of the present invention4XRD pattern of the material.
FIG. 2 shows CoWO prepared in example 1 of the present invention4High power SEM image (a) and low power SEM image (b) of the material.
FIG. 3 shows CoWO prepared in example 1 of the present invention4Material cycling capacity curve.
FIG. 4 shows CoWO prepared in example 2 of the present invention4SEM image of material.
Detailed Description
The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way.
The test methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1:
the chemicals used in this example include sodium tungstate, cobalt nitrate, ammonium fluoride, urea, absolute ethanol, and deionized water.
Carambola-like CoWO with preferred orientation and capacity inverse growth4The preparation method of the microsphere mainly comprises the following steps:
1) accurately weighing 0.13mmol of cobalt nitrate, 0.13mmol of sodium tungstate, 0.4mmol of ammonium fluoride and 0.8mmol of urea, adding deionized water, and preparing into 40ml of uniformly mixed solution under the condition of magnetic stirring;
2) pouring the solution into a 100ml microwave hydrothermal reaction kettle, screwing the reaction kettle and putting the reaction kettle into a microwave reactor, setting the microwave reaction power at 700W, the temperature at 140 ℃ and the reaction time at 60 min. Cooling to room temperature after the reaction is finished, and taking out;
3) respectively ultrasonically and centrifugally cleaning the reacted solution for 3 times by using absolute ethyl alcohol and deionized water, and then drying for 6 hours at the temperature of 60 ℃ in vacuum to obtain CoWO4A precursor;
4) the CoWO to be obtained4Putting the precursor into a muffle furnace for heat treatment, wherein the heat treatment process comprises the steps of heating from room temperature to 400 ℃ at the heating rate of 5 ℃/min under the protection of air, calcining for 2h, and naturally cooling to room temperature to obtain carambola-like CoWO4And (3) microspheres.
FIG. 1 is a CoWO prepared in example 14The X-ray diffraction pattern of the material can see that a whole set of complete diffraction peaks appear at 18.98 degrees, 23.81 degrees, 30.63 degrees, 36.25 degrees, 38.53 degrees, 41.23 degrees, 54.01 degrees and 64.84 degrees, and correspond to CoWO4(JCPDS card No.72-0479) crystal face (100), (011), (-111), (002), (200), (-102), (-221), and (-311), which shows that pure phase CoWO is successfully prepared by the method provided by the invention4. In particular, with the standard CoWO4(JCPDS card No.72-0479) in comparison, the CoWO prepared by the invention4Has (002) preferred orientation growth tendency. The prepared product has the advantages of preferential acquisitionGrowth oriented CoWO4The electrode material has better conductivity.
FIG. 2 is a CoWO prepared in example 1 of the present invention4High power, low power SEM pictures of the material. The results show that CoWO is produced4The electrode material presents the microscopic appearance of the carambola-like microspheres. In particular, CoWO prepared4The multi-level morphology of the cake-carambola microspheres is a cake-shaped morphology with rough surface, which is formed by agglomeration of nano particles, and a plurality of cakes are cut and further assembled into the carambola-like microspheres, wherein the diameter of each cake is 0.8-1.6 mu m, and the thickness of each cake is 100-350 nm; the diameter of the assembled carambola-like microspheres is 1-1.6 mu m.
FIG. 3 shows carambola-like CoWO prepared in example 1 of the present invention4The change curve of the cycling capacity of the microsphere as an electrode material. The CoWO produced can be seen from the figure4The capacity of the electrode material shows a phenomenon that the capacity is firstly obviously increased and then slowly decayed in the whole circulation process, and shows an unconventional phenomenon that the capacity is reversely increased. In particular, in the initial stage of the cycle, CoWO is produced4The specific capacity of the microsphere electrode material is 147.4F g-1/34.8mA h g-1@10A g-1The capacity remained 161.2% after 7000 cycles. The phenomenon of reverse increase of the circulating capacity is caused by the characteristics of a preferred oriented crystal structure and a unique starfruit-like microsphere micro-morphology prepared by the microwave-assisted process.
Example 2:
the drugs used in this example: sodium tungstate, cobalt chloride, ammonium fluoride, urea, absolute ethyl alcohol and deionized water.
Carambola-like CoWO with preferred orientation and capacity inverse growth4The preparation method of the microsphere mainly comprises the following steps:
1) accurately weighing 0.13mmol of cobalt chloride, 0.13mmol of sodium tungstate, 0.4mmol of ammonium fluoride and 0.8mmol of urea, adding deionized water, and preparing into 40ml of uniformly mixed solution under the condition of magnetic stirring;
2) pouring the solution into a 100ml microwave hydrothermal reaction kettle, screwing the reaction kettle and putting the reaction kettle into a microwave reactor, setting the microwave reaction power at 900W, the temperature at 100 ℃ and the reaction time at 30 min. Cooling to room temperature after the reaction is finished, and taking out;
3) respectively ultrasonically and centrifugally cleaning the reacted solution for 3 times by using absolute ethyl alcohol and deionized water, and then drying for 6 hours at the temperature of 60 ℃ in vacuum to obtain CoWO4A precursor;
4) the CoWO to be obtained4Putting the precursor into a muffle furnace for heat treatment, wherein the heat treatment process comprises the steps of heating from room temperature to 400 ℃ at the heating rate of 5 ℃/min under the protection of air, calcining for 2h, and naturally cooling to room temperature to obtain carambola-like CoWO4And (3) microspheres.
FIG. 4 shows CoWO prepared in example 2 of the present invention4SEM photograph of the material. The CoWO produced can be seen from the figure4The material presents the microscopic appearance of the carambola-like microspheres.
It will be apparent to those skilled in the art from this disclosure that many changes and modifications can be made, or equivalents modified, in the embodiments of the invention without departing from the scope of the invention. Therefore, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention shall still fall within the protection scope of the technical solution of the present invention, unless the contents of the technical solution of the present invention are departed.
Claims (10)
1. Carambola-like CoWO with preferred orientation and capacity inverse growth4The preparation method of the microsphere is characterized by mainly comprising the following steps:
1) preparing a precursor: placing an aqueous solution containing a cobalt source and tungstate into a microwave hydrothermal reaction kettle, heating to 100-140 ℃ with the power of 700-1000W, reacting for 25-60 min, centrifuging, washing, and drying to obtain a precursor;
2) carambola-like CoWO4Preparing microspheres: sintering the precursor obtained in the step 1) for 1-5 h at 350-450 ℃ in air atmosphere to obtain carambola-like CoWO4And (3) microspheres.
2. The method according to claim 1, wherein the concentration ratio of cobalt ions to tungstate in the aqueous solution containing a cobalt source and tungstate in step 1) is 1: 1; the concentration of cobalt ion is 1-20 mmol/L.
3. The method according to claim 1, wherein the aqueous solution containing the cobalt source and the tungstate in step 1) further contains ammonium fluoride and urea, wherein the concentration of the ammonium fluoride is 5 to 20mmol/L, and the concentration of the urea is 10 to 40 mmol/L.
4. The method according to claim 1, wherein the cobalt source in step 1) comprises cobalt nitrate, cobalt chloride, cobalt sulfate; the tungstate comprises sodium tungstate and potassium tungstate.
5. The preparation method according to claim 1, wherein the specific washing process in the step 1) is to wash with absolute ethyl alcohol and deionized water for 2-5 times respectively; the drying condition is drying for 2-10 h at 40-80 ℃ under a vacuum condition.
6. The preparation method according to claim 1, wherein the temperature rise rate of the sintering in the step 2) is 1-5 ℃/min.
7. Carambola-like CoWO having preferred orientation and inverse capacity growth, obtained by the preparation method according to any one of claims 1 to 64And (3) microspheres.
8. Carambola-like CoWO according to claim 74Microspheres characterized in that said carambola-like CoWO4The diameter of the microsphere is 1-1.6 μm.
9. Carambola-like CoWO according to claim 74Microspheres characterized in that said carambola-like CoWO4Crystal structure of microsphere and standard CoWO4(JCPDS card No.72-0479) has (002) selectionThe orientation growth tendency is excellent.
10. Carambola-like CoWO as claimed in any one of claims 7 to 94The microspheres are used as electrode materials.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210016375.1A CN114394628B (en) | 2022-01-07 | 2022-01-07 | Carambola-like CoWO with preferential orientation and capacity inverse growth4Microsphere and application thereof |
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