CN112382515A - Oxygen defect T-Nb2O5Preparation method and application - Google Patents
Oxygen defect T-Nb2O5Preparation method and application Download PDFInfo
- Publication number
- CN112382515A CN112382515A CN202011240531.XA CN202011240531A CN112382515A CN 112382515 A CN112382515 A CN 112382515A CN 202011240531 A CN202011240531 A CN 202011240531A CN 112382515 A CN112382515 A CN 112382515A
- Authority
- CN
- China
- Prior art keywords
- oxygen
- deficient
- calcining
- defect
- mixing
- 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.)
- Granted
Links
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 84
- 239000001301 oxygen Substances 0.000 title claims abstract description 84
- 230000007547 defect Effects 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 16
- 238000001354 calcination Methods 0.000 claims abstract description 51
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 49
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000003756 stirring Methods 0.000 claims abstract description 29
- 239000007772 electrode material Substances 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002243 precursor Substances 0.000 claims abstract description 25
- 238000002360 preparation method Methods 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 238000004140 cleaning Methods 0.000 claims abstract description 19
- 238000000227 grinding Methods 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 12
- 229910019804 NbCl5 Inorganic materials 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 230000002950 deficient Effects 0.000 claims description 29
- 239000003990 capacitor Substances 0.000 claims description 25
- 238000001816 cooling Methods 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 17
- 235000019441 ethanol Nutrition 0.000 claims description 15
- 238000006136 alcoholysis reaction Methods 0.000 claims description 8
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 3
- 238000006068 polycondensation reaction Methods 0.000 claims description 3
- 229910001257 Nb alloy Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000010955 niobium Substances 0.000 description 75
- 239000007789 gas Substances 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000004146 energy storage Methods 0.000 description 7
- -1 niobium alkoxide Chemical class 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 229910052758 niobium Inorganic materials 0.000 description 6
- 238000004321 preservation Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 229910003170 M-Nb2O5 Inorganic materials 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000003980 solgel method Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910002625 H-Nb2O5 Inorganic materials 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 238000000935 solvent evaporation Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000007709 nanocrystallization Methods 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention belongs to the technical field of oxygen defect-containing structural materials, and discloses oxygen defect T-Nb2O5Preparation method and application thereof, NbCl5Uniformly mixing with absolute ethyl alcohol to obtain a solution I with the molar concentration of 0.01-0.1 mol/L; mixing deionized water with the solution I, and stirring for 1-2 hours to obtain an opaque sol; placing the sol in a reaction kettle, reacting for 4-12 h at 200 ℃, and cleaning, drying and grinding to obtain a precursor; calcining the precursor for 1-4 h at 600 ℃ in the air atmosphere to obtain the T-Nb containing no oxygen defect2O5(ii) a Mixing T-Nb2O5At H2Calcining for 1-4 h at 600 ℃ in an/Ar atmosphere to obtain oxygen-containing defectsOf (C) T-Nb2O5‑xAnd (3) a supercapacitor electrode material. The method is safe and efficient, low in production cost and low in equipment capital investment, and can well promote T-Nb2O5As the volumetric energy density of the supercapacitor electrode material.
Description
Technical Field
The invention belongs to the technical field of oxygen defect-containing structural materials, and particularly relates to oxygen defect T-Nb2O5A preparation method and application thereof.
Background
At present, a super capacitor is a high-efficiency energy storage device newly emerged in the 70 s of the 20 th century, and the device has the characteristics of quick charge and discharge of a traditional capacitor and also has an energy storage mechanism of an electrochemical battery, so that the super capacitor has high power density and keeps good energy density. Compared with the traditional capacitor, the super capacitor has the characteristics of environmental friendliness, long cycle life, wide working temperature range, high safety and the like, and has great attention in the fields of electric automobiles, military affairs, aviation and the like.
The super capacitor can be mainly classified into an electric double layer capacitor, a pseudo capacitor and a hybrid capacitor according to the difference of energy storage mechanisms of the super capacitor, wherein the energy storage process of the electric double layer capacitor is based on a pure physical mechanism, ions in electrolyte are adsorbed and accumulated at an interface between an electrode and the electrolyte to form a helmholtz electric double layer to store electric charges when polarization is performed, and carbon is a common and most well-studied electrode material of the electric double layer capacitor. In 1975 to 1981, a subject group including Conway, Canada started to use ruthenium oxide (RuO)2) In order to research the Faraday pseudo-capacitance energy storage principle of the representative transition metal oxide electrode material, the material stores energy by performing reversible Faraday reaction on the surface or near surface of the electrode. Ruthenium (Ru) is, however, the least abundant one of the platinum group elements in the earth's crust and is one of the rarest metals, so that although ruthenium oxide was the first to be discovered and has the highest specific capacitance (about 1000F g)-1) The researchers have to try to find other cheap substitutes for the pseudocapacitive material. Bard et al, first treated Nb in 19802O5Research is carried out, and the reaction process of the material has the characteristics of ultra-low volume change, rapid ion transmission channel and the like, and shows excellent electrochemical performanceAnd is considered to be one of the most promising pseudocapacitive electrode materials. T-Nb2O5As an insertion layer type pseudocapacitance electrode material, ions can be embedded into the interlayer of the electrode material, and along with Faraday charge transfer, energy storage and release can be completed through the embedding and the releasing of the ions. Based on Nb5+/Nb4+Redox reaction of (2), T-Nb2O52 Li can occur+The theoretical specific capacity of the catalyst can reach 200 mAh/g. However, T-Nb2O5The industrial application of the method is limited by lower ionic conductivity and electronic conductivity, and the modification methods reported in the literature at present comprise doping, carbon coating and the like, and can improve the electronic conductivity to a certain extent.
Through the above analysis, the problems and defects of the prior art are as follows: T-Nb prepared by the prior art2O5Is limited by the relatively low ionic and electronic conductivity.
The difficulty in solving the above problems and defects is: to solve T-Nb2O5Low conductivity (3X 10)-6S cm-1) The researchers have conducted a great deal of research, and the traditional solid phase method is changed, and the sol-gel method, the anodic oxidation method, the template method and the like are adopted to synthesize T-Nb with different shapes2O5To increase the conductivity, and to combine highly conductive materials such as carbon nanotubes (10)4S cm-1) Isocarbon materials and doping experiments. T-Nb2O5The conductivity of the material is an inherent property of the material, and continuous research and effort are needed to greatly improve the conductivity of the material.
The significance of solving the problems and the defects is as follows: T-Nb2O5As the intercalation pseudocapacitance electrode material, ions can be embedded into the interlayer, so the intercalation pseudocapacitance electrode material can be used for storing sodium ions and serving as a negative electrode of a lithium ion battery besides being used as a supercapacitor electrode material in the aspect of practical application. If T-Nb can be improved2O5The conductivity of the super capacitor and other energy storage devices can be well improved by virtue of the characteristics of ultra-low volume change, rapid ion transmission channels and the like.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides oxygen defect T-Nb2O5A preparation method and application thereof.
The invention is realized by the fact that the oxygen defect T-Nb2O5The oxygen-deficient T-Nb2O5The preparation method comprises the following steps:
step one, NbCl5Mixing with absolute ethyl alcohol, and stirring uniformly to obtain a solution I with the molar concentration of 0.01-0.1 mol/L;
mixing 100-300 parts of deionized water with 400 parts of solution I, and stirring for 1-2 hours to obtain opaque sol;
step three, placing the sol obtained in the step two in a reaction kettle, reacting for 4-12 h at 200 ℃, and cleaning, drying and grinding to obtain a precursor;
step four, calcining the precursor obtained in the step three for 1-4 h at 600 ℃ in the air atmosphere, and cooling to obtain the T-Nb containing no oxygen defect2O5；
Step five, the T-Nb obtained in the step four is used2O5According to the following ratio of 0: 100-20: 80 in the ratio of H2Calcining for 1-4 h at 600 ℃ in an/Ar atmosphere to obtain the oxygen-defect-containing T-Nb2O5-xAnd (3) a supercapacitor electrode material.
Further, the oxygen deficient T-Nb2O5The preparation method comprises the following steps:
(1) reacting NbCl5Mixing with absolute ethyl alcohol, and stirring uniformly to obtain a solution I with the molar concentration of 0.01-0.05 mol/L;
(2) mixing 150-300 parts of deionized water with 400 parts of solution I, and stirring for 1-2 hours to obtain opaque sol;
(3) putting the sol obtained in the step (2) into a reaction kettle, reacting for 6-10 h at 150-200 ℃, and cleaning, drying and grinding to obtain a precursor;
(4) calcining the precursor obtained in the step (3) at 600 ℃ in air atmosphere to be 1 toAfter cooling for 2h, the T-Nb without oxygen defects is obtained2O5；
(5) The T-Nb obtained in the step (4) is2O5According to the following ratio of 0: 100-20: 80 in the ratio of H2Calcining for 1-2 h at 600 ℃ in an/Ar atmosphere to obtain the oxygen-defect-containing T-Nb2O5-xAnd (3) a supercapacitor electrode material.
Further, the cleaning comprises two steps of water cleaning and alcohol cleaning, and the gel is formed through alcoholysis reaction, hydrolysis reaction and polycondensation reaction, so that impurities such as HCl are generated, and two steps of cleaning and removing are needed.
Another object of the present invention is to provide a method for producing a T-Nb strain using the oxygen deficient strain2O5The method for preparing the obtained T-Nb-containing no oxygen defect2O5Said oxygen defect-free T-Nb2O5The appearance is conventional granular, and the grain diameter is 15 nm.
Another object of the present invention is to provide a method for producing a T-Nb strain using the oxygen deficient strain2O5The preparation method of (1) prepares oxygen-containing defective T-Nb2O5-xSaid oxygen-deficient T-Nb2O5-xThe particles of (A) are uniform, the particle size is 20-50 nm, and the BET specific surface area is 39.60m2The current density of the current per gram can reach 907.9mAh/cm3Volume to capacity of (a).
Another object of the present invention is to provide a T-Nb strain free from oxygen deficiency2O5The application in the preparation of electrode materials of super capacitors.
Another object of the present invention is to provide an oxygen-deficient T-Nb2O5-xThe application in the preparation of electrode materials of super capacitors.
By combining all the technical schemes, the invention has the advantages and positive effects that: in the present invention NbCl is added5Mixing with absolute ethyl alcohol, stirring uniformly to obtain a solution I with the molar concentration of 0.01-0.1 mol/L, wherein the solution I is mixed with the absolute ethyl alcohol to form gel by alcoholysis reaction, and the molar concentration of 0.01-0.1 mol/L is the optimal material ratio, so that raw materials can be utilized to the maximum extent, and the production efficiency is improved(ii) a Adding 150-300 parts of deionized water can promote alcoholysis, accelerate gel formation and shorten experimental flow; the optimal reaction temperature is 150-200 ℃, gel cannot be produced when the temperature is lower than 150 ℃, and the danger coefficient of the experiment can be increased when the temperature is higher than 200 ℃ for a reaction kettle. The calcination temperature must be kept at 600 ℃, and the excessive high or low temperature can cause other crystal forms of Nb2O5(H-Nb2O5、M-Nb2O5And TT-Nb2O5) Is generated. If the calcination time is too short, the target product cannot be fully synthesized, and if the calcination time is too long, grains grow abnormally, so that the performance of the sample is adversely affected. H2The ratio of/Ar is 0: 100-20: 80 for optimum calcination atmosphere, H2Too much oxygen defects of the synthesized target product are excessive, and even collapse of a three-dimensional structure is caused, so that adverse effects are generated; h2Too little will result in insignificant oxygen defects and will not contribute to the improvement of the properties of the target product.
The oxygen defect T-Nb provided by the invention2O5The preparation method of (1) and the synthesis of T-Nb by utilizing a solvent heat-assisted sol-gel method2O5Initial NbCl5A series of alcoholysis and hydrolysis reactions occur in the mixed solvent of ethanol and water to produce Nb (OC)2H5)nCl5-nAnd Nb (OH) (OC)2H5)4When niobium alkoxide is used, the niobium alkoxide is difficult to form gel under the general sol-gel condition, so that the subsequent experiment promotes the dealcoholization condensation of the niobium alkoxide under the catalytic action of temperature and pressure to form a three-dimensional network structure, a solvent losing fluidity is filled among the structures, the gel with a stable three-dimensional structure is obtained through high-temperature aging and solvent evaporation, and the T-Nb with the nano particles can be obtained through one-step calcination2O5The calcination temperature must be kept at 600 ℃, and if the temperature is too high or too low, other crystal forms of Nb can be caused2O5(H-Nb2O5、M-Nb2O5And TT-Nb2O5) Is generated. The preparation method is safe and efficient, low in production cost and low in equipment capital investment, and can well promote T-Nb2O5As capacitor electrode materialsVolumetric energy density.
The method of combining the atmosphere deoxidation method and the heating hydrogenation method is adopted to generate the oxygen vacancy, the generation efficiency of the oxygen vacancy can be greatly improved, and partial oxygen can be generated from T-Nb in the Ar atmosphere environment by utilizing the principle of the equilibrium between two phases of oxygen at a contact interface2O5Precipitation with H in the atmosphere2Water is generated by combination, so that oxygen can be continuously precipitated, and a target product, namely the T-Nb containing oxygen defects can be obtained after calcining for 1h2O5-x。
The invention adopts the method of oxygen vacancy to improve T-Nb2O5The volume specific capacity of the alloy is calculated by combining the first principle, and the oxygen vacancy can be proved to improve the T-Nb simultaneously2O5The ionic conductivity and the electronic conductivity of the composite material can improve the electrochemical dynamics of the composite material under the condition of not sacrificing the volume ratio of the active material, and greatly improves the T-Nb2O5Volume to capacity of (a).
Compared with other inventions, the invention also has the following outstanding advantages:
the raw materials used in the method are pollution-free, and the whole synthesis process is free of waste which is difficult to degrade, so that the method is green and environment-friendly; the invention improves the conventional sol-gel preparation method, adopts solvent heat to assist and promote the formation of gel, and enlarges the application scale of the sol-gel method.
The invention changes the traditional material modification mode (structural nanocrystallization, doping, cladding and the like), and prepares the T-Nb containing oxygen defects2O5-xThe super capacitor prepared by using the super capacitor as an electrode material improves the ionic conductivity and the electronic conductivity, thereby having higher volume specific capacity and cycle performance, and can reach 907.9mAh/cm under the current density of 10mA/g3Volume to capacity of (a).
Drawings
FIG. 1 is an oxygen deficient T-Nb provided by an embodiment of the present invention2O5The preparation method of (1) is a flow chart.
FIG. 2 is an oxygen deficient T-Nb strain provided by an embodiment of the present invention2O5-xCharge-discharge cycle curve schematic of the prepared supercapacitorFigure (a).
FIG. 3 is an oxygen deficient T-Nb alloy according to an embodiment of the present invention2O5-xFirst-principle computation graph.
FIG. 4(a) is a diagram of oxygen defect-free T-Nb provided in an example of the present invention2O5Schematic representation of a transmission electron micrograph.
FIG. 4(b) is an oxygen-deficient T-Nb strain according to an embodiment of the present invention2O5-xSchematic representation of a transmission electron micrograph.
FIG. 5(a) is a diagram of oxygen defect-free T-Nb provided in an example of the present invention2O5And oxygen-deficient T-Nb2O5-xX-ray diffraction pattern of (a).
FIG. 5(b) is a diagram showing oxygen defect-free T-Nb strain according to an example of the present invention2O5And oxygen-deficient T-Nb2O5-xAn X-ray photoelectron spectrum of (a).
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Aiming at the problems in the prior art, the invention provides oxygen defect T-Nb2O5The invention also discloses a preparation method and application thereof, which are described in detail in the following with reference to the accompanying drawings.
As shown in FIG. 1, the oxygen deficient T-Nb provided by the embodiment of the invention2O5The preparation method comprises the following steps:
s101, mixing NbCl5Mixing with absolute ethyl alcohol, and stirring uniformly to obtain a solution I with the molar concentration of 0.01-0.1 mol/L;
s102, mixing 100-300 parts of deionized water with 400 parts of solution I, and stirring for 1-2 hours to obtain opaque sol;
s103, placing the sol obtained in the step S102 in a reaction kettle, reacting for 4-12 h at 200 ℃, and cleaning, drying and grinding to obtain a precursor;
s104, calcining the precursor obtained in the step S103 at 600 ℃ in an air atmosphere for 1-4 h, and cooling to obtain the T-Nb containing no oxygen defect2O5；
S105, the T-Nb obtained in the S1042O5At H2Calcining at 600 ℃ for 1-4 h in an atmosphere of/Ar (0: 100-20: 80) to obtain the oxygen-defect-containing T-Nb2O5-xAnd (3) a supercapacitor electrode material.
In the step S101 provided by the embodiment of the invention, the molar concentration of the solution I is 0.01-0.1 mol/L; the concentration is the optimal proportion of the raw materials, and the raw materials can be utilized to the maximum extent. Under the concentration, the precursor can be optimally prepared, the yield is high, and the prepared precursor has moderate particle size.
The addition of 150-200 parts of water in step S102 provided by the embodiment of the invention can promote the formation of sol, the stirring time is 1-2 h, the stirring time is short, reactions such as alcoholysis and the like cannot be sufficiently carried out, and the sol is not uniformly formed.
The reaction temperature of the step S103 provided by the embodiment of the invention is 200 ℃, if the reaction temperature is lower, the effect of promoting the formation of the gel is not obvious, and if the reaction temperature is higher, the energy consumption is higher, and meanwhile, certain potential safety hazard is brought.
The reaction time of the step S103 provided by the embodiment of the invention is 4-12 h, if the heat preservation time is too short, the gel is not sufficiently formed, the preparation of the precursor is not favorable, and if the heat preservation time is too long, the three-dimensional space network structure formed by the gel is damaged, the granularity of the target product is influenced, and the energy consumption is also increased.
The preparation method of the supercapacitor electrode material provided by the embodiment of the invention comprises the following steps:
(1) reacting NbCl5Mixing with absolute ethyl alcohol, and uniformly stirring to obtain a mixture with a molar concentration of (5) and a calcination temperature and a heat preservation time consistent with those in the step (4);
(2) mixing 100-300 parts of deionized water with 400 parts of the solution I, and stirring for 1-2 hours to obtain an opaque sol;
(3) putting the sol obtained in the step (2) into a reaction kettle, reacting for 4-12 h at 200 ℃, and cleaning, drying and grinding to obtain a precursor;
(4) calcining the precursor obtained in the step (3) for 1-4 h at 600 ℃ in an air atmosphere, and cooling to obtain the T-Nb containing no oxygen defect2O5；
(5) The T-Nb obtained in the step (4) is2O5At H2Calcining at 600 ℃ for 1-4 h in an atmosphere of/Ar (0: 100-20: 80) to obtain the oxygen-defect-containing T-Nb2O5-xAnd (3) a supercapacitor electrode material.
The cleaning in the step (3) provided by the embodiment of the invention needs two steps of water cleaning and alcohol cleaning, and the formation of gel needs alcoholysis reaction, hydrolysis reaction and polycondensation reaction, which can generate HCl and other impurities, and needs two steps of cleaning and removing. Grinding is used for preparing the next step of calcination, and the particle size after calcination can be more uniform through grinding.
The calcination temperature in the step (4) provided by the embodiment of the invention is 600 ℃, the calcination temperature is high, and H-Nb can be generated2O5And M-Nb2O5TT-Nb is formed at a low calcination temperature2O5The synthesis of target products is not facilitated, and the generated impure phases are increased, so that the performance of the prepared electrode material is greatly reduced, and the volume energy density and the application of the electrode material in a super capacitor are influenced.
The heat preservation time of the step (4) provided by the embodiment of the invention is 1-4 h, if the heat preservation time is short, the reaction can not be fully carried out, and the precursor can not be completely generated into T-Nb2O5And the resulting T-Nb2O5The crystal grains can not grow normally, and the generated T-Nb can be generated by long heat preservation time2O5The abnormal growth of crystal grains makes the granularity of the target product larger and uneven, and increases the energy consumption. Preferably, the calcination temperature and the holding time in step (5) are the same as those in step (4).
The first calcining atmosphere provided by the embodiment of the invention is air to obtain the T-Nb without oxygen defect2O5The second calcining atmosphere is H2A mixed gas of/Ar (0: 100 to 20: 80), H2Mixing with Ar favors obtaining oxygen-deficient T-Nb2O5。
The T-Nb prepared by the preparation method does not contain oxygen defects2O5The shape is conventional granular, and the grain diameter is about 15 nm. Further calcining the resulting oxygen-deficient T-Nb2O5-xThe particles are uniform, the particle size is about 30nm, the dense stacking is facilitated, and the BET specific surface area is 39.60m2/g。
The technical solution of the present invention is further described below with reference to the principle.
The invention synthesizes T-Nb by using a solvent heat-assisted sol-gel method2O5Initial NbCl5A series of alcoholysis and hydrolysis reactions occur in the mixed solvent of ethanol and water to produce Nb (OC)2H5)nCl5-nAnd Nb (OH) (OC)2H5)4When niobium alkoxide is used, the niobium alkoxide is difficult to form gel under the general sol-gel condition, so that the subsequent experiment promotes the dealcoholization condensation of the niobium alkoxide under the catalytic action of temperature and pressure to form a three-dimensional network structure, a solvent losing fluidity is filled among the structures, the gel with a stable three-dimensional structure is obtained through high-temperature aging and solvent evaporation, and the T-Nb with the nano particles can be obtained through one-step calcination2O5The calcination temperature must be kept at 600 ℃, and if the temperature is too high or too low, other crystal forms of Nb can be caused2O5(H-Nb2O5、M-Nb2O5And TT-Nb2O5) Is generated.
The technical solution of the present invention is further described with reference to the following examples.
Example 1
Mixing 2mmol of NbCl and 40ml of ethanol, stirring for 15min to obtain a colorless solution, adding 10ml of water, stirring for 1h, placing in a reaction kettle, keeping the temperature at 200 ℃ for 8h, naturally cooling to obtain gel, washing with water and ethanol for multiple times, drying, and grinding. Calcining the fully ground precursor for 1h at 600 ℃ in the air atmosphere, and naturally cooling to obtain the T-Nb free of oxygen defects2O5Changing the atmosphere for further calcination, secondThe atmosphere of the secondary calcination is H2The mixed gas of/Ar (5: 95) is calcined to obtain the target product, namely the T-Nb containing oxygen defects2O5。
Fig. 3 is a graph showing the result of the first principle calculation, and it can be seen that the forbidden band width gradually narrows to disappear at last with the increase of oxygen vacancies, and the conductivity is greatly enhanced. Transmission electron micrograph thereof
As shown in FIG. 4, it can be seen that synthesized oxygen-deficient T-Nb2O5The particle size is uniform and is 20-45 nm. The generation of oxygen vacancies resulted in a corresponding decrease in the binding energy of Nb in the crystal, and FIG. 5(b) is an XPS plot of the sample, with the blue region having a decrease in binding energy from 211.1eV to the right to 210.1eV, illustrating the generation of oxygen vacancies.
Example 2
Mixing 4mmol of NbCl with 40ml of ethanol, stirring for 15min to obtain a colorless solution, adding 15ml of water, stirring for 2h, placing in a reaction kettle, keeping the temperature at 200 ℃ for 8h, naturally cooling to obtain gel, washing with water and ethanol for multiple times, drying, and grinding. Calcining the fully ground precursor for 2h at 600 ℃ in the air atmosphere, and naturally cooling to obtain the T-Nb free of oxygen defects2O5The particle size is about 20 nm. Changing gas atmosphere for further calcination, wherein the second calcination atmosphere is H2The target product, namely the T-Nb containing oxygen defects is obtained after the calcination of the mixed gas of/Ar (10: 90)2O5The particle size is about 30 nm.
Example 3
Mixing 1mmol NbCl with 40ml ethanol, stirring for 15min to obtain colorless solution, adding 10ml water, stirring for 1h, placing in a reaction kettle, keeping the temperature at 200 deg.C for 8h, naturally cooling to obtain gel, washing with water and ethanol for several times, oven drying, and grinding. Calcining the fully ground precursor for 2h at 600 ℃ in the air atmosphere, and naturally cooling to obtain the T-Nb free of oxygen defects2O5The particle size is about 20 nm. Changing gas atmosphere for further calcination, wherein the second calcination atmosphere is H2Mixed gas of/Ar (10: 90), sinteringAfter the reaction, the target product, namely the T-Nb containing oxygen defects is obtained2O5The particle size is about 40 nm.
Example 4
Mixing 3mmol NbCl with 40ml ethanol, stirring for 15min to obtain colorless solution, adding 10ml water, stirring for 1h, placing in a reaction kettle, keeping the temperature at 200 ℃ for 12h, naturally cooling to obtain gel, washing with water and ethanol for multiple times, drying, and grinding. Calcining the fully ground precursor for 3h at 600 ℃ in the air atmosphere, and naturally cooling to obtain the T-Nb free of oxygen defects2O5The particle size is about 20 nm. Changing gas atmosphere for further calcination, wherein the second calcination atmosphere is H2The mixed gas of/Ar (0: 100) is calcined to obtain the target product, namely the T-Nb containing oxygen defects2O5The particle size is about 50 nm.
Example 5
Mixing 3mmol NbCl and 50ml ethanol, stirring for 15min to obtain colorless solution, adding 10ml water, stirring for 1h, placing in a reaction kettle, keeping the temperature at 200 ℃ for 4h, naturally cooling to obtain gel, washing with water and ethanol for multiple times, drying, and grinding. Calcining the fully ground precursor for 4h at 600 ℃ in the air atmosphere, and naturally cooling to obtain the T-Nb free of oxygen defects2O5The particle size is about 20 nm. Changing gas atmosphere for further calcination, wherein the second calcination atmosphere is H2The mixed gas of/Ar (20: 80) is calcined to obtain the target product, namely the T-Nb containing oxygen defects2O5The particle size is about 45 nm.
Performance testing
Oxygen-deficient T-Nb from example 12O5The super capacitor is prepared by taking the super capacitor as an electrode material, and the preparation method comprises the following steps:
the T-Nb obtained in example 12O5-xAs an electrode active material, a material prepared by mixing polyvinylidene fluoride (PVDF) as a binder and acetylene black as a conductive agent in a weight ratio of 80: 10: 10, adding 1-methyl-2-pyrrolidone (NMP), stirring to form slurry, and coatingAnd drying the copper foil surface for 12 hours at 85 ℃ to obtain the electrode plate. And pressing the electrode slice by a roller press, then placing the electrode slice in a vacuum oven to dry for 8 hours at 90 ℃, and cutting to prepare the super capacitor positive plate.
The prepared electrode plates are assembled into a button cell (CR2032) for testing, a metal lithium plate is used as a negative electrode of the cell, and 1.0M LiPF6And (EC: DMC ═ 3: 7) is used as electrolyte to fill the whole battery, a microporous polypropylene film is used as a diaphragm between the positive plate and the negative plate, a spring plate and a gasket are added to assemble the battery, after 24 hours of placement, constant-current charge-discharge cycle test is carried out at the constant temperature of 20 ℃ and at the current density of 10mA/g, and the charge-discharge voltage is 1-3V.
The test results are shown in FIG. 2, and the oxygen-defective T-Nb obtained by the invention2O5-xThe super capacitor prepared for the anode material has higher volume energy density which can reach 907.9mAh/cm under the current density of 10mA/g3Volume to capacity of (a).
The above description is only for the purpose of illustrating the present invention and the appended claims are not to be construed as limiting the scope of the invention, which is intended to cover all modifications, equivalents and improvements that are within the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. Oxygen defect T-Nb2O5Characterized in that the oxygen-deficient T-Nb is2O5The preparation method comprises the following steps:
reacting NbCl5Mixing with absolute ethyl alcohol, and stirring uniformly to obtain a solution I;
mixing deionized water with the solution I, and stirring to obtain an opaque sol;
placing the obtained sol in a reaction kettle for reaction, and cleaning, drying and grinding to obtain a precursor;
calcining the obtained precursor in air atmosphere, and cooling to obtain the T-Nb containing no oxygen defect2O5；
Will be describedThe obtained T-Nb2O5In proportion of H2Calcining in an Ar atmosphere to obtain the oxygen-defect-containing T-Nb2O5-xAnd (3) a supercapacitor electrode material.
2. Oxygen deficient T-Nb according to claim 12O5Is characterized in that the preparation method is
Step one, NbCl5Mixing with absolute ethyl alcohol, and stirring uniformly to obtain a solution I with the molar concentration of 0.01-0.1 mol/L;
mixing 100-300 parts of deionized water with 400 parts of solution I, and stirring for 1-2 hours to obtain opaque sol;
step three, placing the sol obtained in the step two in a reaction kettle, reacting for 4-12 h at 200 ℃, and cleaning, drying and grinding to obtain a precursor;
step four, calcining the precursor obtained in the step three for 1-4 h at 600 ℃ in the air atmosphere, and cooling to obtain the T-Nb containing no oxygen defect2O5；
Step five, the T-Nb obtained in the step four is used2O5According to the following ratio of 0: 100-20: 80 in the ratio of H2Calcining for 1-4 h at 600 ℃ in an/Ar atmosphere to obtain the oxygen-defect-containing T-Nb2O5-xAnd (3) a supercapacitor electrode material.
3. Oxygen deficient T-Nb according to claim 22O5Characterized in that NbCl is added5Mixing with absolute ethyl alcohol, and stirring uniformly to obtain a solution I with the molar concentration of 0.01-0.05 mol/L;
and mixing 150-300 parts of deionized water with 400 parts of the solution I, and stirring for 1-2 hours to obtain an opaque sol.
4. Oxygen deficient T-Nb according to claim 22O5The preparation method is characterized in that the obtained sol is placed in a reaction kettle, reacts for 6-10 hours at the temperature of 150-200 ℃, and is cleaned, dried and ground to obtain the solA precursor;
calcining the obtained precursor for 1-2 h at 600 ℃ in the air atmosphere, and cooling to obtain the T-Nb free of oxygen defects2O5。
5. Oxygen deficient T-Nb according to claim 22O5Characterized in that the obtained T-Nb is subjected to2O5According to the following ratio of 0: 100-5: 95 in the ratio H2Calcining for 1-2 h at 600 ℃ in an/Ar atmosphere to obtain the oxygen-defect-containing T-Nb2O5-xAnd (3) a supercapacitor electrode material.
6. The oxygen-deficient T-Nb as claimed in any one of claims 1 to 52O5The preparation method is characterized in that the cleaning comprises two steps of water cleaning and alcohol cleaning, the gel is formed through alcoholysis reaction, hydrolysis reaction and polycondensation reaction to generate HCl impurities, and two steps of cleaning and removing are needed.
7. Use of the oxygen deficient T-Nb of any one of claims 1 to 52O5The method for preparing the obtained T-Nb-containing no oxygen defect2O5Characterized in that the oxygen-deficient-free T-Nb content2O5The appearance is conventional granular, and the grain diameter is 15 nm.
8. Use of the oxygen deficient T-Nb of any one of claims 1 to 32O5The preparation method of (1) prepares oxygen-containing defective T-Nb2O5-xCharacterized in that said oxygen-deficient T-Nb2O5-xThe particles of (A) are uniform, the particle size is 20-50 nm, and the BET specific surface area is 39.60m2The current density of the current per gram can reach 907.9mAh/cm3Volume to capacity of (a).
9. The oxygen defect-free T-Nb alloy of claim 72O5The application in the preparation of electrode materials of super capacitors.
10. Oxygen-deficient T-Nb in accordance with claim 82O5-xThe application in the preparation of electrode materials of super capacitors.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011240531.XA CN112382515B (en) | 2020-11-09 | 2020-11-09 | Oxygen defect T-Nb 2 O 5-x Preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011240531.XA CN112382515B (en) | 2020-11-09 | 2020-11-09 | Oxygen defect T-Nb 2 O 5-x Preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112382515A true CN112382515A (en) | 2021-02-19 |
| CN112382515B CN112382515B (en) | 2022-08-19 |
Family
ID=74579121
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011240531.XA Active CN112382515B (en) | 2020-11-09 | 2020-11-09 | Oxygen defect T-Nb 2 O 5-x Preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112382515B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113134349A (en) * | 2021-04-21 | 2021-07-20 | 岭南生态文旅股份有限公司 | Blue layered Nb2O5Preparation method and application of photocatalyst |
| CN114774980A (en) * | 2022-05-10 | 2022-07-22 | 浙江工业大学 | Vanadium oxide catalyst containing different valence states formed by controlling different calcination conditions, and synthesis method and application thereof |
| CN114864916A (en) * | 2022-06-30 | 2022-08-05 | 武汉理工大学三亚科教创新园 | Niobium pentoxide coated graphite composite negative electrode material and preparation method thereof |
| CN114899018A (en) * | 2022-06-21 | 2022-08-12 | 贵州大学 | Supercapacitor with conjugate configuration and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103855386A (en) * | 2014-03-21 | 2014-06-11 | 西北有色金属研究院 | Fe-doped Nb2Ox nano porous material with oxygen deficiency structure and application |
| CN107768663A (en) * | 2017-09-28 | 2018-03-06 | 芜湖恒尼动力电池材料科技有限公司 | The method for preparing the transition metal oxide with oxygen defect |
| KR20190042955A (en) * | 2017-10-17 | 2019-04-25 | 인하대학교 산학협력단 | Nanocomposite comprising 3-dimensional porous carbon nanowbs and niobium oxide |
| CN109767925A (en) * | 2019-02-22 | 2019-05-17 | 扬州大学 | T-Nb for lithium ion super capacitor2O5/ egg white carbon composite and preparation method thereof |
| CN110606508A (en) * | 2018-06-17 | 2019-12-24 | 深圳格林德能源有限公司 | Novel negative electrode material preparation method and solid-state lithium ion battery thereof |
| CN111082040A (en) * | 2019-12-19 | 2020-04-28 | 上海交通大学 | Core-shell structure T-Nb2O5Preparation method and application of @ C composite material |
| CN111725490A (en) * | 2020-06-11 | 2020-09-29 | 武汉工程大学 | Nitrogen-doped carbon-coated superfine niobium pentoxide nanocomposite and preparation method thereof |
-
2020
- 2020-11-09 CN CN202011240531.XA patent/CN112382515B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103855386A (en) * | 2014-03-21 | 2014-06-11 | 西北有色金属研究院 | Fe-doped Nb2Ox nano porous material with oxygen deficiency structure and application |
| CN107768663A (en) * | 2017-09-28 | 2018-03-06 | 芜湖恒尼动力电池材料科技有限公司 | The method for preparing the transition metal oxide with oxygen defect |
| KR20190042955A (en) * | 2017-10-17 | 2019-04-25 | 인하대학교 산학협력단 | Nanocomposite comprising 3-dimensional porous carbon nanowbs and niobium oxide |
| CN110606508A (en) * | 2018-06-17 | 2019-12-24 | 深圳格林德能源有限公司 | Novel negative electrode material preparation method and solid-state lithium ion battery thereof |
| CN109767925A (en) * | 2019-02-22 | 2019-05-17 | 扬州大学 | T-Nb for lithium ion super capacitor2O5/ egg white carbon composite and preparation method thereof |
| CN111082040A (en) * | 2019-12-19 | 2020-04-28 | 上海交通大学 | Core-shell structure T-Nb2O5Preparation method and application of @ C composite material |
| CN111725490A (en) * | 2020-06-11 | 2020-09-29 | 武汉工程大学 | Nitrogen-doped carbon-coated superfine niobium pentoxide nanocomposite and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| LINZHEN LOU ETC: "Facile fabrication of interconnected-mesoporous TNb2O5 nanofibers as anodes for lithium-ion batteries", 《SCIENCE CHINA MATERIALS.》 * |
| M. GOTIC´ ETC: "Sol–gel synthesis and characterization of V2O5 powders", 《MATERIALS LETTERS》 * |
| TAIMUR ATHAR ETC: "One-Pot Synthesis and Characterization of Nb2O5 Nanopowder", 《JOURNAL OF NANOSCIENCE AND NANOTECHNOLOGY》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113134349A (en) * | 2021-04-21 | 2021-07-20 | 岭南生态文旅股份有限公司 | Blue layered Nb2O5Preparation method and application of photocatalyst |
| CN113134349B (en) * | 2021-04-21 | 2023-02-03 | 岭南生态文旅股份有限公司 | Blue layered Nb 2 O 5 Preparation method and application of photocatalyst |
| CN114774980A (en) * | 2022-05-10 | 2022-07-22 | 浙江工业大学 | Vanadium oxide catalyst containing different valence states formed by controlling different calcination conditions, and synthesis method and application thereof |
| CN114774980B (en) * | 2022-05-10 | 2023-11-21 | 浙江工业大学 | Catalyst containing vanadium oxide with different valence states and synthesis method and application thereof |
| CN114899018A (en) * | 2022-06-21 | 2022-08-12 | 贵州大学 | Supercapacitor with conjugate configuration and preparation method thereof |
| CN114899018B (en) * | 2022-06-21 | 2023-12-05 | 贵州大学 | Super capacitor with conjugated configuration and preparation method thereof |
| CN114864916A (en) * | 2022-06-30 | 2022-08-05 | 武汉理工大学三亚科教创新园 | Niobium pentoxide coated graphite composite negative electrode material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112382515B (en) | 2022-08-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112382515B (en) | Oxygen defect T-Nb 2 O 5-x Preparation method and application | |
| Sun et al. | Carbon-coated mesoporous LiTi2 (PO4) 3 nanocrystals with superior performance for lithium-ion batteries | |
| CN109659540B (en) | Preparation method of porous carbon-coated antimony telluride nanosheet and application of porous carbon-coated antimony telluride nanosheet as negative electrode material of metal ion battery | |
| CN109767925B (en) | T-Nb for lithium ion super capacitor2O5Egg white carbon composite material and preparation method thereof | |
| Li et al. | Hetero-structured NiS2/CoS2 nanospheres embedded on N/S co-doped carbon nanocages with ultra-thin nanosheets for hybrid supercapacitors | |
| Feng et al. | NiO Flowerlike porous hollow nanostructures with an enhanced interfacial storage capability for battery-to-pseudocapacitor transition | |
| CN111463022A (en) | Preparation method of cobalt molybdenum oxide/nickel cobalt phosphide composite material | |
| CN109473649B (en) | Composite negative electrode material of sodium-ion battery and preparation method thereof | |
| CN109616651B (en) | Heteroatom-doped graphene-based vanadium sodium phosphate composite nano material for sodium ion anode material | |
| CN106299344B (en) | A kind of sodium-ion battery nickel titanate negative electrode material and preparation method thereof | |
| CN111048754B (en) | Tin-doped rutile TiO2Preparation method and application of composite material | |
| Zhang et al. | Flaky N-doped hard carbon anode material for sodium-ion batteries | |
| Wei et al. | Biomass derived fibrous porous carbon loaded zinc oxide nanoparticles as high-performance anode materials for lithium ion batteries | |
| Song et al. | Ultra-thin mesoporous LiV3O8 nanosheet with exceptionally large specific area for fast and reversible Li storage in lithium-ion battery cathode | |
| Yu et al. | Ni0. 85Se anchored on N-doped MoSe2 hybrids for long-life asymmetric supercapacitors | |
| Liu et al. | A more economical choice for the cathode material of Ni-MH batteries with high electrochemical performances: 3D flower-like Ni–Fe LDHs | |
| CN108640167B (en) | Preparation method of two-dimensional nanosheet | |
| CN114639809B (en) | Composite hard carbon negative electrode material, preparation method and application | |
| CN106207251B (en) | Carbon coating method of hydrothermal lithium iron phosphate | |
| CN112820866B (en) | Capsule-shaped nickel ferrite composite carbon skeleton lithium ion battery cathode material and preparation method and application thereof | |
| CN112251812B (en) | Single crystal NaNbO3Cube, preparation method and application thereof | |
| CN114792606A (en) | Carbon-loaded manganese-doped sodium titanate energy storage material, preparation method and application thereof, and negative electrode plate | |
| CN110061196A (en) | A kind of method of the modified lithium cobaltate cathode material of surface doping | |
| CN111341567B (en) | 3D poplar catkin derived carbon-supported NiCo-LDH nanosheet supercapacitor and preparation method thereof | |
| Varalakshmi et al. | Improved supercapacitive performance of low pore size and highly stable nanostructured NiCo2O4 electrodes |
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 |