CN114394628B - Carambola-like CoWO with preferential orientation and capacity inverse growth4Microsphere and application thereof - Google Patents
Carambola-like CoWO with preferential orientation and capacity inverse growth4Microsphere and application thereof Download PDFInfo
- Publication number
- CN114394628B CN114394628B CN202210016375.1A CN202210016375A CN114394628B CN 114394628 B CN114394628 B CN 114394628B CN 202210016375 A CN202210016375 A CN 202210016375A CN 114394628 B CN114394628 B CN 114394628B
- Authority
- CN
- China
- Prior art keywords
- cowo
- microsphere
- tungstate
- carambola
- starchy
- 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.)
- Active
Links
- 239000004005 microsphere Substances 0.000 claims abstract description 54
- 239000007772 electrode material Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- 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
- 230000035484 reaction time Effects 0.000 claims description 3
- 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
- 230000000630 rising effect Effects 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims 1
- 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
- 239000000463 material Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000013078 crystal Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 235000010082 Averrhoa carambola Nutrition 0.000 description 2
- 241000544051 Damasonium alisma Species 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 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
- 230000002238 attenuated effect Effects 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
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- ZXOKVTWPEIAYAB-UHFFFAOYSA-N dioxido(oxo)tungsten Chemical group [O-][W]([O-])=O ZXOKVTWPEIAYAB-UHFFFAOYSA-N 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
- 238000003912 environmental pollution Methods 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
- 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
- 239000000126 substance Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/30—Sulfides
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
- Y02E60/13—Energy storage using capacitors
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a carambola-like CoWO 4 microsphere with preferred orientation and capacity reverse growth and application thereof, and belongs to the technical field of electrode materials. The micro-morphology of the starlike CoWO 4 microsphere is a starlike microsphere with rough surface, in particular to a disk-like morphology formed by agglomerating nano particles, and a plurality of disks are assembled in a tangent way, wherein the disk-like diameter is 0.8-1.6 mu m, and the disk thickness is 100-350 nm; the diameter of the assembled carambola-like microsphere is 1-1.6 mu m, the carambola-like CoWO 4 microsphere provided by the invention has (002) preferential orientation as an electrode material, and the specific capacitance has inverse growth characteristic in the 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 a carambola-like CoWO 4 microsphere with preferred orientation and capacity reverse growth and application thereof.
Background
The shortage of fossil fuels and the harm to environmental pollution force people to develop novel energy storage devices which are green and renewable. Among the energy storage devices, supercapacitors and lithium ion batteries are widely researched by virtue of the advantages of high power density, high energy density, low preparation cost, green environment 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 and quick synthesis and low cost becomes a current research hot spot.
Cobalt tungstate (CoWO 4) with a wolframite structure is taken as an important p-type transition metal oxide, has excellent electrochemical activity and more electronic multi-valence conductivity, and is widely focused in the fields of sensors, magnetism, catalysis, electrochemical energy storage batteries and the like. The microcosmic appearance and the crystal structure obviously influence the performance of the CoWO 4 electrode material, and researchers prepare the CoWO 4 electrode material with various appearances, such as nanowires, nanoflower, nanorods, nanoparticles and the like, through a solid phase method, coprecipitation, hydrothermal method and other technological methods. However, the synthesis method and the product generally have the problems of complex preparation process, easy agglomeration of the product, poor uniformity and the like, so that the electrochemical performance of the prepared CoWO 4 electrode material is not ideal.
Disclosure of Invention
In view of the above, the application provides a carambola-like CoWO 4 microsphere with preferred orientation and capacity inverse growth and application thereof, the application prepares the carambola-like CoWO 4 microsphere by means of a microwave auxiliary process, and the prepared CoWO 4 microsphere has the advantages of unique microscopic morphology, good crystal structure, easy, efficient and rapid synthesis, low cost and the like; the development process of the micro-spherical shape of the similar starfruit CoWO 4 prepared based on the microwave-assisted hydrothermal process is a CoWO 4 nano particle nucleation stage, a round cake shape stage with irregular growth surface roughness, and a phase of tangential self-assembly of a plurality of round cakes into similar starfruit micro-spheres; the formation of the morphology and the characteristics of a preferred orientation crystal structure are that the formation is generated by utilizing the characteristic of microwave heating and rapidly heating to the reaction temperature (100-140 ℃) under the power condition of 700-1000W.
The technical scheme of the invention is as follows:
The preparation method of the carambola-like CoWO 4 microsphere with preferred orientation and capacity inverse growth 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, heating to 100-140 ℃ for 5-10 min with power of 700-1000W, centrifuging, washing and drying to obtain a precursor;
2) Preparation of starchy CoWO 4 -like microspheres: sintering the precursor obtained in the step 1) for 1-5 hours at 350-450 ℃ in air atmosphere to obtain the carambola-like CoWO 4 microsphere.
Further, in the step 1), the concentration ratio of cobalt ions to tungstate in the aqueous solution containing the cobalt source and the tungstate is 1:1.
Further, the concentration of cobalt ions in step 1) is 1-20mmol/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 10-40mmol/L.
Further, the cobalt source in step 1) comprises cobalt nitrate, cobalt chloride and cobalt sulfate; the tungstate comprises sodium tungstate and potassium tungstate.
Further, the specific process of the washing in the step 1) is to use absolute ethyl alcohol and deionized water to wash for 2-5 times respectively.
Further, the drying condition in the step 1) is that the drying is carried out for 2-10 hours at 40-80 ℃ under vacuum condition.
Further, the temperature rising speed of the sintering in the step 2) is 1-5 ℃/min.
In another aspect, the invention provides the carambola-like CoWO 4 microsphere with preferential orientation and capacity inverse growth prepared by the method.
Further, the micro-morphology of the starlike CoWO 4 microsphere is starlike micro-spheres, specifically nano-particles are agglomerated into a cake-like morphology, a plurality of cakes are assembled in a tangent way to form the starlike micro-spheres, wherein the diameter of the cake-like micro-spheres is 0.8-1.6 mu m, and the thickness of the cake-like micro-spheres is 100-350 nm; the diameter of the assembled starlike microspheres is 1-1.6 mu m.
Further, the crystal structure of the carambola-like CoWO 4 microsphere has a (002) preferential orientation growth tendency compared with that of the standard CoWO 4 (JCPCDS card No. 72-0479).
The invention also provides application of the starchy CoWO 4 -like microsphere as an electrode material.
Further, the specific capacitance of the electrode material exhibited an inverse growth characteristic during cycling, the initial specific capacitance was 147.4F g -1/34.8mA h g-1@10A g-1, and the capacity remained 161.2% after 7000 cycles.
Further, the electrode material comprises electrode materials of lithium ion batteries and supercapacitors.
Compared with the prior art, the invention has the beneficial effects that:
1) Compared with the common hydrothermal method, the preparation method of the starlike CoWO 4 microsphere with preferred orientation and capacity inverse growth is simple and convenient to operate, low in cost, short in experimental period (shortened to 1/16-1/5 of that of other processes), strong in controllability, low in reaction temperature and duration, free of adjustment of the pH value of a precursor, excellent in microcosmic appearance of the CoWO 4 microsphere electrode material, good in crystal structure, higher in purity, better in dispersibility, capable of inverse growth and circulation capacity and excellent in electrochemical performance.
2) The microscopic morphology of the CoWO 4 microsphere is a multi-stage carambola-like microsphere with a rough surface, specifically, nano particles are agglomerated into a round cake-like morphology, a plurality of round cakes are assembled tangentially to form the carambola-like microsphere, and compared with the standard CoWO 4 (JCPCDS card No. 72-0479), the crystal structure of the carambola-like microsphere has a (002) preferred orientation growth trend.
3) The specific capacitance of the starlike CoWO 4 microsphere as an electrode material has inverse growth characteristic in the cyclic process, the initial specific capacitance is 147.4F g -1/34.8mA h g-1@10A g-1, and the capacity is kept to 161.2% after 7000 cycles.
4) The CoWO 4 microsphere material with the (002) preferred orientation crystal structure has better conductivity, and meanwhile, the specific capacity inverse growth phenomenon of the CoWO 4 microsphere electrode material shows excellent structural stability, and the CoWO 4 microsphere material as an electrode material of an energy storage device such as a lithium ion battery and a super capacitor shows excellent electrochemical performance, and can meet the commercial application performance index of the energy storage device.
Drawings
In order to more clearly describe the technical solutions in the embodiments of the present invention, the drawings that are required to be used in the embodiments will be briefly described.
FIG. 1 is an XRD pattern of CoWO 4 material prepared in example 1 of the present invention.
FIG. 2 shows a high-magnification SEM image (a) and a low-magnification SEM image (b) of a CoWO 4 material prepared in example 1 according to the present invention.
FIG. 3 is a graph showing the cycle capacity change of the CoWO 4 material prepared in example 1 of the present invention.
FIG. 4 is an SEM image of the CoWO 4 material prepared in example 2 of the present invention.
Detailed Description
The following non-limiting examples will enable those of ordinary skill in the art to more fully understand the invention and are not intended to limit the invention in any way.
The test methods described in the following examples, unless otherwise specified, are all conventional; the reagents and materials, unless otherwise specified, are commercially available.
Example 1:
The medicines used in this example include sodium tungstate, cobalt nitrate, ammonium fluoride, urea, absolute ethyl alcohol, and deionized water.
The preparation method of the carambola-like CoWO 4 microsphere with preferred orientation and capacity inverse growth 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 40ml of uniformly mixed solution under the magnetic stirring condition;
2) Pouring the solution into a 100ml microwave hydrothermal reaction kettle, screwing the reaction kettle, and putting the reaction kettle into a microwave reactor, wherein the microwave reaction power is set to be 700W, the temperature is 140 ℃, and the reaction time is 60min. Cooling to room temperature after the reaction is finished, and taking out;
3) Respectively ultrasonically centrifuging and cleaning the reacted solution with absolute ethyl alcohol and deionized water for 3 times, and then drying the solution for 6 hours at the temperature of 60 ℃ in vacuum to obtain a precursor of CoWO 4;
4) And (3) putting the obtained CoWO 4 precursor into a muffle furnace for heat treatment, wherein the heat treatment process is to heat up to 400 ℃ from room temperature at a heating rate of 5 ℃/min under the protection of air, calcining for 2 hours, and naturally cooling to room temperature to obtain the starlike CoWO 4 microsphere.
FIG. 1 shows the X-ray diffraction pattern of the CoWO 4 material prepared in example 1, and shows that a complete set of diffraction peaks appear at 18.98 °, 23.81 °, 30.63 °, 36.25 °, 38.53 °, 41.23 °, 54.01 °, 64.84 °, corresponding to crystal planes (100), (011), (-111), (002), (200), (-102), (-221), (-311) of CoWO 4 (JCPCDS card No. 72-0479), which illustrate that the method provided by the invention successfully prepares pure-phase CoWO 4. In particular, compared with the standard CoWO 4 (JCPCDS card No. 72-0479), the CoWO 4 prepared by the invention has the preferred orientation growth trend of (002). The CoWO 4 electrode material with preferred orientation growth prepared by the invention has better conductivity.
FIG. 2 is a high-magnification, low-magnification SEM photograph of CoWO 4 material prepared in example 1 of the present invention. The results show that the prepared CoWO 4 electrode material presents a microscopic morphology similar to that of the carambola-shaped microspheres. Specifically, the prepared CoWO 4 is a multi-level morphology of a cake-carambola microsphere, firstly, a cake morphology with a rough surface is formed by agglomeration of nano particles, a plurality of cakes are tangent and further assembled into a carambola-like microsphere, wherein the diameter of the cake is 0.8-1.6 mu m, and the thickness of the cake is 100-350 nm; the diameter of the assembled carambola-like microsphere is 1-1.6 mu m.
FIG. 3 is a graph showing the cycle capacity change of the starchy CoWO 4 -like microspheres as electrode materials prepared in example 1 of the present invention. It can be seen from the figure that the prepared CoWO 4 electrode material shows the phenomenon that the capacity is obviously increased firstly and then slowly attenuated in the whole cycle process, and shows the phenomenon that the unconventional capacity is inversely increased. Specifically, in the initial stage of the cycle, the specific capacity of the prepared CoWO 4 microsphere electrode material was 147.4F g -1/34.8mA h g-1@10A g-1, and the capacity was kept at 161.2% after 7000 cycles. The phenomenon of the reverse increase of the circulation capacity is caused by the characteristics of the crystal structure with preferred orientation and the unique micro morphology of the carambola-like microsphere prepared by the microwave auxiliary procedure.
Example 2:
The medicine used in this example: sodium tungstate, cobalt chloride, ammonium fluoride, urea, absolute ethyl alcohol and deionized water.
The preparation method of the carambola-like CoWO 4 microsphere with preferred orientation and capacity inverse growth 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 40ml of uniformly mixed solution under the magnetic stirring condition;
2) Pouring the solution into a 100ml microwave hydrothermal reaction kettle, screwing the reaction kettle, and putting the reaction kettle into a microwave reactor, wherein the microwave reaction power is set to be 900W, the temperature is 100 ℃, and the reaction time is 30min. Cooling to room temperature after the reaction is finished, and taking out;
3) Respectively ultrasonically centrifuging and cleaning the reacted solution with absolute ethyl alcohol and deionized water for 3 times, and then drying for 6 hours at the temperature of 60 ℃ in vacuum to obtain a CoWO 4 precursor;
4) And (3) putting the obtained CoWO 4 precursor into a muffle furnace for heat treatment, wherein the heat treatment process is to heat up to 400 ℃ from room temperature at a heating rate of 5 ℃/min under the protection of air, calcining for 2 hours, and naturally cooling to room temperature to obtain the starlike CoWO 4 microsphere.
FIG. 4 is an SEM photograph of CoWO 4 material prepared in example 2 of the present invention. From the figure, it can be seen that the prepared CoWO 4 material presents a microscopic morphology like that of the starfruit-like microspheres.
Many possible variations and modifications of the disclosed technology can be made by anyone skilled in the art without departing from the scope of the technology, or the technology can be modified to be equivalent. Therefore, any simple modification, equivalent variation and modification of the above embodiments according to the technical substance of the present invention shall still fall within the scope of the technical solution of the present invention.
Claims (8)
1. The preparation method of the carambola-like CoWO 4 microsphere with preferred orientation and capacity inverse growth 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 a temperature of 100-140 ℃ with a power of 700-1000W, and performing centrifugation, washing and drying for a reaction time of 25-60 min to obtain a precursor;
2) Preparation of starchy CoWO 4 -like microspheres: sintering the precursor obtained in the step 1) for 1-5 hours at 350-450 ℃ in an air atmosphere to obtain a carambola-like CoWO 4 microsphere;
The concentration ratio of cobalt ions to tungstate in the aqueous solution containing the cobalt source and the tungstate in the step 1) is 1:1, a step of; the concentration of cobalt ions is 1-20mmol/L;
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 10-40mmol/L.
2. The method of claim 1, wherein the cobalt source in step 1) comprises cobalt nitrate, cobalt chloride, cobalt sulfate; the tungstate comprises sodium tungstate and potassium tungstate.
3. The preparation method according to claim 1, wherein the specific washing process in step 1) is to use absolute ethyl alcohol and deionized water to wash for 2-5 times respectively; and the drying condition is that the drying is carried out for 2-10 hours at the temperature of 40-80 ℃ under the vacuum condition.
4. The preparation method according to claim 1, wherein the temperature rising rate of sintering in step 2) is 1-5 ℃/min.
5. The starchy CoWO 4 -like microsphere with a preferential orientation and a capacity inverse growth produced by the method of any one of claims 1-4.
6. The starchy CoWO 4 -like microsphere as defined in claim 5, wherein the diameter of the starchy CoWO 4 -like microsphere is 1-1.6 μm.
7. The starchy cooo 4 -like microsphere of claim 5, wherein the crystalline structure of the starchy cooo 4 -like microsphere has a (002) preferential orientation growth trend compared to JCPDS card No. 72-0479 of standard cooo 4.
8. Use of the starchy cooo 4 -like microspheres according to any one of claims 5 to 7 as electrode material.
Priority Applications (1)
| 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 |
Applications Claiming Priority (1)
| 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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114394628A CN114394628A (en) | 2022-04-26 |
| CN114394628B true CN114394628B (en) | 2024-05-17 |
Family
ID=81228897
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210016375.1A Active CN114394628B (en) | 2022-01-07 | 2022-01-07 | Carambola-like CoWO with preferential orientation and capacity inverse growth4Microsphere and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114394628B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103880086A (en) * | 2014-03-10 | 2014-06-25 | 江苏大学 | Synthetic method of tungstate based on tungsten oxide as precursor |
| CN103991913A (en) * | 2014-05-29 | 2014-08-20 | 陕西科技大学 | Method for preparing CoWO4 nano powder material by adopting microwave-hydrothermal method |
| CN106315695A (en) * | 2016-08-24 | 2017-01-11 | 福州大学 | Strawberry like Ni-Co nano material and preparing method thereof |
| CN108059194A (en) * | 2017-12-19 | 2018-05-22 | 扬州大学 | Spherical CoWO4The preparation method of nano material and its application in electro-catalysis |
| CN108190969A (en) * | 2018-03-01 | 2018-06-22 | 广东工业大学 | A kind of preparation method of cobalt sulfide nano material |
| CN110289175A (en) * | 2019-07-12 | 2019-09-27 | 大连海事大学 | A kind of high capacity NiMn2O4Micron ball/foamed nickel electrode material and its preparation method and application |
| CN110776016A (en) * | 2019-09-29 | 2020-02-11 | 河北科技大学 | Method for synthesizing electrode material cobalt tungstate for super capacitor |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8968534B2 (en) * | 2012-01-31 | 2015-03-03 | Toyota Motor Egineering & Manufacturing North America, Inc. | Water oxidation catalyst |
| US10040050B2 (en) * | 2014-10-30 | 2018-08-07 | Toyota Motor Engineering & Manufacturing North America, Inc. | Microwave synthesis of cobalt tungstate for use as stable oxygen evolution catalyst |
-
2022
- 2022-01-07 CN CN202210016375.1A patent/CN114394628B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103880086A (en) * | 2014-03-10 | 2014-06-25 | 江苏大学 | Synthetic method of tungstate based on tungsten oxide as precursor |
| CN103991913A (en) * | 2014-05-29 | 2014-08-20 | 陕西科技大学 | Method for preparing CoWO4 nano powder material by adopting microwave-hydrothermal method |
| CN106315695A (en) * | 2016-08-24 | 2017-01-11 | 福州大学 | Strawberry like Ni-Co nano material and preparing method thereof |
| CN108059194A (en) * | 2017-12-19 | 2018-05-22 | 扬州大学 | Spherical CoWO4The preparation method of nano material and its application in electro-catalysis |
| CN108190969A (en) * | 2018-03-01 | 2018-06-22 | 广东工业大学 | A kind of preparation method of cobalt sulfide nano material |
| CN110289175A (en) * | 2019-07-12 | 2019-09-27 | 大连海事大学 | A kind of high capacity NiMn2O4Micron ball/foamed nickel electrode material and its preparation method and application |
| CN110776016A (en) * | 2019-09-29 | 2020-02-11 | 河北科技大学 | Method for synthesizing electrode material cobalt tungstate for super capacitor |
Non-Patent Citations (4)
| Title |
|---|
| CoWO4微晶的制备及性能研究;何秀娟;陕西科技大学硕士论文;20151203;全文 * |
| Synthesis of some transtion MWO4 (M: Mn, Fe, Co, Ni, Cu, Zn, Cd) nanostructures by hydrothermal method);Saeid pourmasoud, et al;Journal or materials science: Materials in elextronics;20190422;第30卷;8105-8144 * |
| 低温熔盐法制备纳米钨酸钴;宋祖伟;孙虎元;李旭云;孙立娟;王巍;臧贝妮;;无机盐工业;20100310(03);全文 * |
| 具有分级结构的Co_3O_4绣球花状微米球的构筑及其锂离子电池负极性能研究;魏磊;王伟;;山东科学;20171215(06);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114394628A (en) | 2022-04-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110723737B (en) | Wool ball type Ti3C2Preparation method and application of (MXene) nano material | |
| CN102942223B (en) | Preparation method of hexagonal flaky NH4V3O8 microcrystals | |
| CN110233058B (en) | Self-assembled hollow NiCo2S4 material, preparation method and application thereof | |
| US20240140818A1 (en) | Preparation method and application of amorphous metal oxide hollow multi-shell material | |
| CN111099650A (en) | CeO2Molten salt method for synthesizing nano spherical particles | |
| CN107611359A (en) | The preparation method of lithium ion battery Ni NiO/ graphene composite negative poles | |
| CN105060351A (en) | Flower-like cobaltosic oxide material composed of nanoparticles and preparation method thereof | |
| CN111816866B (en) | Method for preparing lithium-rich manganese-based positive electrode material by co-precipitation-hydrothermal combination | |
| CN105198007A (en) | Preparation and stripping methods of mesoporous cobaltosic oxide nanosheet | |
| CN105271443B (en) | Method for preparing flaky nano CoO or Co3O4 through assistant microwave heating | |
| CN107500356B (en) | A kind of preparation method of nano-particles self assemble vanadic anhydride microballoon positive electrode | |
| CN114394628B (en) | Carambola-like CoWO with preferential orientation and capacity inverse growth4Microsphere and application thereof | |
| CN106887580B (en) | A kind of lithium ion battery negative material and preparation method thereof | |
| CN108091838B (en) | Method for preparing core-shell structure nano α -Fe2O3@ C composite material in one step | |
| CN115305053B (en) | Cerium-based hollow nano wave-absorbing material and preparation method and application thereof | |
| CN108483513B (en) | Preparation method of three-dimensional flower-like cobaltosic oxide | |
| CN114349041B (en) | Preparation method of zinc sulfide and cobalt sulfide core-shell cube nanomaterial suitable for sodium ion battery electrode | |
| CN108573815A (en) | The preparation method of electrode material for super capacitor porous spherical NiO | |
| CN113381004A (en) | Preparation method of vanadium pentoxide in-situ coated NCM111 ternary cathode material | |
| CN112331842A (en) | Molybdenum dioxide nanoparticle/carbon assembled zigzag nano hollow sphere material and preparation and application thereof | |
| CN112838209A (en) | Preparation method of transition metal oxide @ carbon composite nanomaterial with core-shell structure | |
| CN113800563B (en) | NbO microsphere and hydrothermal synthesis method and application thereof | |
| Peng et al. | Low temperature deep eutectic solvents-assisted synthesis of amorphous MnO2 cathode for zinc ion batteries | |
| CN111333110B (en) | Silver-copper-vanadium-oxygen compound nano material and preparation method and application thereof | |
| CN108511730B (en) | Porous netted Zn2Ti3O8/TiO2Nano composite flaky particle 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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |