CN113772728A - Mixed-phase niobium-titanium oxide, and preparation method and energy storage application thereof - Google Patents
Mixed-phase niobium-titanium oxide, and preparation method and energy storage application thereof Download PDFInfo
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- OBOYOXRQUWVUFU-UHFFFAOYSA-N [O-2].[Ti+4].[Nb+5] Chemical compound [O-2].[Ti+4].[Nb+5] OBOYOXRQUWVUFU-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000004146 energy storage Methods 0.000 title claims abstract description 10
- 239000002243 precursor Substances 0.000 claims abstract description 27
- 238000004729 solvothermal method Methods 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 18
- 238000012983 electrochemical energy storage Methods 0.000 claims abstract description 11
- 150000002821 niobium Chemical class 0.000 claims abstract description 11
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 10
- 150000003608 titanium Chemical class 0.000 claims abstract description 8
- 239000007772 electrode material Substances 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims abstract description 4
- 239000011259 mixed solution Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 32
- 238000001354 calcination Methods 0.000 claims description 22
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 22
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 10
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 claims description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 9
- 229910052786 argon Inorganic materials 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
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 8
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- XFHGGMBZPXFEOU-UHFFFAOYSA-I azanium;niobium(5+);oxalate Chemical compound [NH4+].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XFHGGMBZPXFEOU-UHFFFAOYSA-I 0.000 claims description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 claims description 2
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 claims 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims 1
- 239000011540 sensing material Substances 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 10
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 10
- 239000003990 capacitor Substances 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 229910001275 Niobium-titanium Inorganic materials 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- RJSRQTFBFAJJIL-UHFFFAOYSA-N niobium titanium Chemical compound [Ti].[Nb] RJSRQTFBFAJJIL-UHFFFAOYSA-N 0.000 abstract 1
- 238000004886 process control Methods 0.000 abstract 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 12
- 238000004321 preservation Methods 0.000 description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
- 238000002156 mixing Methods 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 229910010379 TiNb2O7 Inorganic materials 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- 239000011232 storage material Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 239000012982 microporous membrane Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
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- -1 polypropylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
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- 238000009792 diffusion process Methods 0.000 description 1
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- 238000003487 electrochemical reaction Methods 0.000 description 1
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- 238000009830 intercalation Methods 0.000 description 1
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- 238000005468 ion implantation Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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- 230000009897 systematic effect Effects 0.000 description 1
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- C01G33/00—Compounds of niobium
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- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
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- 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
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
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Abstract
本发明公开了一种混合相铌钛氧化物及其制备方法与储能应用，是首先配制含有金属铌盐、金属钛盐的混合溶液，通过溶剂热法制备结晶度低的铌钛前驱体，然后通过高温煅烧获得结晶度高且形貌、物相均可调控的混合相铌钛氧化物。本发明所得混合相铌钛氧化物能够应用于制备锂离子电容器等电化学储能器件的电极材料，其中各物相的协同储能作用可进一步提高材料的电化学性能；本发明的制备方法简单、成本低、过程易于控制，可以批量化生产。
The invention discloses a mixed-phase niobium-titanium oxide and its preparation method and energy storage application. First, a mixed solution containing metal niobium salt and metal titanium salt is prepared, and a niobium-titanium precursor with low crystallinity is prepared by a solvothermal method. Then, the mixed-phase niobium-titanium oxide with high crystallinity and controllable morphology and phase is obtained by high-temperature calcination. The mixed-phase niobium-titanium oxide obtained in the invention can be applied to the preparation of electrode materials for electrochemical energy storage devices such as lithium ion capacitors, wherein the synergistic energy storage effect of each phase can further improve the electrochemical performance of the material; the preparation method of the invention is simple , Low cost, easy process control, and mass production.
Description
Technical Field
The invention belongs to the field of preparation of nano functional materials, and particularly relates to a mixed-phase niobium titanium oxide, and a preparation method and an energy storage application thereof.
Background
In recent years, niobium-titanium oxide has attracted much attention in the fields of electrochemical energy storage, environmental catalysis, gas sensing and the like by virtue of its advantages of excellent physicochemical properties, abundant structural compositions, nontoxicity, abundant sources and the like. Especially when applied to electrochemical energy storage, the deintercalation type niobium titanium oxide with high working potential and theoretical capacity is an ideal negative electrode material: firstly, the rapid ion intercalation/deintercalation process of niobium-titanium oxide can effectively make up the difference of the internal electrochemical reaction kinetics of the energy storage device; secondly, the niobium-titanium oxide with relatively high working potential can simultaneously avoid the formation of SEI film and lithium dendrite, thereby ensuring the safety of the electrode; moreover, the niobium-titanium oxide can provide a wider ion diffusion channel, so that the structure of the niobium-titanium oxide is not changed before and after ion implantation, and the structural stability and the cycling stability of the niobium-titanium oxide are enhanced. However, the low intrinsic ion mobility and conductivity of niobium-titanium oxide seriously affect the rate capability thereof, thereby restricting the wide application thereof in the field of electrochemical energy storage.
On the basis of abundant niobium-titanium oxide structure composition, further construction of mixed-phase niobium-titanium oxide is one of effective means for improving electrochemical performance of niobium-titanium oxide. Compared with a single phase, the mixture phase can provide more redox couples and active centers, the energy storage characteristics of the components of each phase are fully utilized, and the electrochemical performance of the active material can be further improved through synergistic effect. However, similar niobium-titanium oxides reported at present generally involve a relatively complex preparation process, so that exploring a simple preparation method of the niobium-titanium oxide and realizing systematic regulation and control of the morphology, phase and performance of the niobium-titanium oxide have important effects on further improving the electrochemical performance of the niobium-titanium oxide and expanding the application field of the niobium-titanium oxide.
Disclosure of Invention
Based on the problems in the prior art, the invention discloses a mixed-phase niobium titanium oxide, a preparation method and an energy storage application thereof, and aims to obtain a high-performance electrochemical energy storage material with adjustable and controllable morphology, phase and performance by a simple method.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention discloses a preparation method of mixed-phase niobium-titanium oxide, which is characterized by comprising the following steps: firstly, preparing a mixed solution containing metal niobium salt and metal titanium salt, preparing a precursor by a solvothermal method, and then calcining at high temperature to obtain the mixed-phase niobium-titanium oxide with high crystallinity and adjustable morphology and phase. The method specifically comprises the following steps:
(1) preparing a precursor by a solvothermal method: weighing 0-5.0 mmol of metal niobium salt and 0-1.2 mmol of metal titanium salt, and dissolving in 5-50 mL of organic solvent to obtain a solution A; weighing 0.3-10 mmol of hexamethylenetetramine and dissolving in 50-150 mL of deionized water to obtain a solution B; adding the solution B into the solution A, uniformly mixing, carrying out a solvothermal reaction at a solvothermal temperature of 100-200 ℃ for 5-60 h, centrifuging, washing with water, drying, and collecting a powder product to obtain a precursor;
(2) preparing mixed-phase niobium-titanium oxide by high-temperature calcination: placing the precursor in a tube furnace, and calcining at high temperature under the protection of argon, wherein the calcining temperature is 500-900 ℃, the heat preservation time is 30-600 min, and the heating rate is 0.5-10 ℃ for min-1And naturally cooling to room temperature after the calcination is finished, thus obtaining the mixed-phase niobium-titanium oxide.
Further, the metal niobium salt is at least one of niobium chloride, niobium oxalate and ammonium niobium oxalate, and the metal titanium salt is at least one of titanium isopropoxide, titanyl sulfate, titanium tetrachloride, tetrabutyl titanate and n-butyl titanate.
Further, the organic solvent in the step (1) is one or a mixture of any more of ethanol, methanol, ethylene glycol, N-dimethylformamide and N-methylpyrrolidone.
According to the method, the morphology and the phase composition of the obtained mixed-phase niobium-titanium oxide can be regulated and controlled by regulating the molar ratio of the metal niobium salt to the metal titanium salt, so that the electrochemical energy storage characteristic of the obtained mixed-phase niobium-titanium oxide can be regulated and controlled.
The mixed-phase niobium-titanium oxide can be used as an electrode material of electrochemical energy storage materials such as lithium ion capacitors, lithium ion batteries and sodium ion batteries, and the mixed-phase niobium-titanium oxide can show higher specific capacity and excellent rate capability when used as an electrode material of a lithium ion capacitor. In addition, the mixed-phase niobium-titanium oxide has great application potential in the fields of catalysis, sensing and the like.
The invention has the beneficial effects that:
1. the preparation method is simple, low in cost, easy to control in process and capable of realizing batch production; the mixed-phase niobium-titanium oxide prepared by the method has higher specific capacity and excellent rate capability, and has better application prospect in the fields of electrochemical energy storage materials and the like.
2. The preparation method can realize synchronous optimization of the morphology, phase composition and electrochemical performance of the mixed-phase niobium-titanium oxide by regulating and controlling the molar ratio of the metal niobium salt to the metal titanium salt, for example, when the molar ratio of niobium chloride to titanium isopropoxide is 2:1 (1.8mmol of niobium pentachloride and 0.9mmol of titanium isopropoxide), the obtained product has a nano-sheet structure, and the phase composition is TiO2/TiNb2O7And the electrochemical performance is optimal.
Drawings
FIG. 1 is a FESEM photograph of mixed phase niobium titanium oxide obtained in example 1;
FIG. 2 is a FESEM photograph of mixed phase niobium titanium oxide obtained in example 2;
FIG. 3 is a FESEM photograph of mixed phase niobium titanium oxide obtained in example 3;
FIG. 4 is a FESEM photograph of mixed phase niobium titanium oxide obtained in example 4;
FIG. 5 is a FESEM photograph of mixed phase niobium titanium oxide obtained in example 5;
FIG. 6 is a FESEM photograph of mixed phase niobium titanium oxide obtained in example 6;
FIG. 7 is an XRD spectrum of mixed phase niobium titanium oxide obtained in examples 1 to 6;
FIG. 8 is a graph showing rate capability of mixed phase niobium titanium oxide obtained in examples 1 to 6;
FIG. 9 is a graph of the power density versus energy density for a lithium ion capacitor assembled with the mixed phase niobium titanium oxide prepared in example 4 as the negative electrode.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein, but rather should be construed as broadly as the present invention is capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Example 1
A preparation method of mixed-phase niobium-titanium oxide specifically comprises the following steps:
(1) preparing a precursor by a solvothermal method: weighing 1.8mmol niobium pentachloride and dissolving in 22.5mL N-methyl pyrrolidone to obtain a solution A; 7.2mmol of hexamethylenetetramine was weighed and dissolved in 67.5mL of deionized water to obtain solution B. And adding the solution B into the solution A, uniformly mixing, carrying out a solvothermal reaction, wherein the solvothermal temperature is 200 ℃, the heat preservation time is 24 hours, then centrifuging, washing with water, drying, and collecting a powder product to obtain a precursor.
(2) Preparing mixed-phase niobium-titanium oxide by high-temperature calcination: placing the precursor in a tube furnace, and calcining at high temperature under the protection of argonCalcining at 750 deg.C for 300min at 2 deg.C for 2 min-1And naturally cooling to room temperature after the calcination is finished to obtain the mixed-phase niobium titanium oxide, wherein the FESEM photograph of the mixed-phase niobium titanium oxide is shown in figure 1.
Example 2
A preparation method of mixed-phase niobium-titanium oxide specifically comprises the following steps:
(1) preparing a precursor by a solvothermal method: weighing 1.8mmol of niobium pentachloride and 0.3mmol of titanium isopropoxide, and dissolving in 22.5mL of N-methylpyrrolidone to obtain a solution A; 7.2mmol of hexamethylenetetramine was weighed and dissolved in 67.5mL of deionized water to obtain solution B. And adding the solution B into the solution A, uniformly mixing, carrying out a solvothermal reaction, wherein the solvothermal temperature is 200 ℃, the heat preservation time is 24 hours, then centrifuging, washing with water, drying, and collecting a powder product to obtain a precursor.
(2) Preparing mixed-phase niobium-titanium oxide by high-temperature calcination: placing the precursor in a tube furnace, and calcining at high temperature under the protection of argon, wherein the calcining temperature is 750 ℃, the heat preservation time is 300min, and the heating rate is 2 ℃ for min-1And naturally cooling to room temperature after the calcination is finished to obtain the mixed-phase niobium titanium oxide, wherein the FESEM photograph of the mixed-phase niobium titanium oxide is shown in figure 2.
Example 3
A preparation method of mixed-phase niobium-titanium oxide specifically comprises the following steps:
(1) preparing a precursor by a solvothermal method: weighing 1.8mmol of niobium pentachloride and 0.6mmol of titanium isopropoxide, and dissolving in 22.5mL of N-methylpyrrolidone to obtain a solution A; 7.2mmol of hexamethylenetetramine was weighed and dissolved in 67.5mL of deionized water to obtain solution B. And adding the solution B into the solution A, uniformly mixing, carrying out a solvothermal reaction, wherein the solvothermal temperature is 200 ℃, the heat preservation time is 24 hours, then centrifuging, washing with water, drying, and collecting a powder product to obtain a precursor.
(2) Preparing mixed-phase niobium-titanium oxide by high-temperature calcination: placing the precursor in a tube furnace, and calcining at high temperature under the protection of argon, wherein the calcining temperature is 750 ℃, the heat preservation time is 300min, and the heating rate is 2 ℃ for min-1Naturally cooling to the temperature after calcinationAt room temperature, mixed-phase niobium titanium oxide is obtained, and the FESEM photograph is shown in figure 3.
Example 4
A preparation method of mixed-phase niobium-titanium oxide specifically comprises the following steps:
(1) preparing a precursor by a solvothermal method: weighing 1.8mmol of niobium pentachloride and 0.9mmol of titanium isopropoxide, and dissolving in 22.5mL of N-methylpyrrolidone to obtain a solution A; 7.2mmol of hexamethylenetetramine was weighed and dissolved in 67.5mL of deionized water to obtain solution B. And adding the solution B into the solution A, uniformly mixing, carrying out a solvothermal reaction, wherein the solvothermal temperature is 200 ℃, the heat preservation time is 24 hours, then centrifuging, washing with water, drying, and collecting a powder product to obtain a precursor.
(2) Preparing mixed-phase niobium-titanium oxide by high-temperature calcination: placing the precursor in a tube furnace, and calcining at high temperature under the protection of argon, wherein the calcining temperature is 750 ℃, the heat preservation time is 300min, and the heating rate is 2 ℃ for min-1And naturally cooling to room temperature after the calcination is finished to obtain the mixed-phase niobium titanium oxide, wherein the FESEM photograph of the mixed-phase niobium titanium oxide is shown in figure 4.
Example 5
A preparation method of mixed-phase niobium-titanium oxide specifically comprises the following steps:
(1) preparing a precursor by a solvothermal method: weighing 1.8mmol of niobium pentachloride and 1.8mmol of titanium isopropoxide, and dissolving in 22.5mL of N-methylpyrrolidone to obtain a solution A; 7.2mmol of hexamethylenetetramine was weighed and dissolved in 67.5mL of deionized water to obtain solution B. And adding the solution B into the solution A, uniformly mixing, carrying out a solvothermal reaction, wherein the solvothermal temperature is 200 ℃, the heat preservation time is 24 hours, then centrifuging, washing with water, drying, and collecting a powder product to obtain a precursor.
(2) Preparing mixed-phase niobium-titanium oxide by high-temperature calcination: placing the precursor in a tube furnace, and calcining at high temperature under the protection of argon, wherein the calcining temperature is 750 ℃, the heat preservation time is 300min, and the heating rate is 2 ℃ for min-1And naturally cooling to room temperature after the calcination is finished to obtain the mixed-phase niobium titanium oxide, wherein the FESEM photograph of the mixed-phase niobium titanium oxide is shown in figure 5.
Example 6
A preparation method of mixed-phase niobium-titanium oxide specifically comprises the following steps:
(1) preparing a precursor by a solvothermal method: weighing 1.8mmol of titanium isopropoxide, and dissolving the titanium isopropoxide in 22.5mL of N-methylpyrrolidone to obtain a solution A; 7.2mmol of hexamethylenetetramine was weighed and dissolved in 67.5mL of deionized water to obtain solution B. And adding the solution B into the solution A, uniformly mixing, carrying out a solvothermal reaction, wherein the solvothermal temperature is 200 ℃, the heat preservation time is 24 hours, then centrifuging, washing with water, drying, and collecting a powder product to obtain a precursor.
(2) Preparing mixed-phase niobium-titanium oxide by high-temperature calcination: placing the precursor in a tube furnace, and calcining at high temperature under the protection of argon, wherein the calcining temperature is 750 ℃, the heat preservation time is 300min, and the heating rate is 2 ℃ for min-1And naturally cooling to room temperature after the calcination is finished to obtain the mixed-phase niobium titanium oxide, wherein the FESEM photograph of the mixed-phase niobium titanium oxide is shown in figure 6.
Referring to the above examples, the present inventors investigated the effect of different ratios of niobium pentachloride and titanium isopropoxide on the morphology and phase of mixed phase niobium titanium oxide. As can be seen from FIGS. 1 to 6, the samples of the other examples all have a nano-sheet structure, except that the sample of example 6 is in a granular form. The phase characterization of XRD in FIG. 7 shows that the phase compositions of the materials obtained in examples 1-6 are Nb2O5、TiNb2O7/Nb2O5、TiNb2O7/Nb2O5、TiO2/TiNb2O7、TiO2/TiNb2O7And TiO2。
In order to test the performance of the mixed-phase niobium titanium oxide obtained in the above examples as an electrochemical energy storage material, the mixed-phase niobium titanium oxide was prepared as an electrode material of a lithium ion capacitor and subjected to electrochemical test as follows:
assembling the half cell: dispersing the material synthesized in the embodiment 1-6, conductive agent carbon black and adhesive polyvinylidene fluoride in N-methyl pyrrolidone according to the mass ratio of 8:1:1, uniformly mixing to obtain slurry, and coating the slurry on a copper foil to prepare an electrode plate; to dissolve in Ethylene Carbonate (EC) and carbonic acid1.0mol L of dimethyl ester (DMC) (volume ratio 1:1)-1LiPF6And a 2320 type polypropylene microporous membrane is taken as a diaphragm, and the diaphragm is assembled into a 2032 type button battery in an argon glove box. Constant current charge and discharge test is carried out through an LAND CT-2001A test system, wherein the selected voltage range is 1.0-3.0V (V vs. Li/Li)+) Current density of 0.1A g-1、0.2A g-1、0.5A g-1、1.0A g-1、2.0A g-1、5.0A g-1、10.0A g-1。
Assembling a lithium ion capacitor: using the mixed-phase niobium titanium oxide obtained in example 4 as a negative electrode and activated carbon as a positive electrode, 1.0mol L of the mixed-phase niobium titanium oxide dissolved in Ethylene Carbonate (EC) and dimethyl carbonate (DMC) (volume ratio 1:1) was added-1LiPF6Assembling a lithium ion capacitor by using a 2320 type polypropylene microporous membrane as a diaphragm as an electrolyte, and performing constant current charge and discharge test by using a CHI 760E electrochemical workstation, wherein the selected voltage range is 0-4.0V, and the current density is 0.1A g-1、0.2A g-1、0.5A g-1、1.0A g-1、2.0A g-1。
FIG. 8 is a graph showing the rate capability of six mixed-phase niobium titanium oxides prepared in examples 1 to 6, wherein the phase composition obtained in example 4 is TiO2/TiNb2O7The mixed-phase niobium-titanium oxide has the highest specific capacity and the optimal rate capability, and the specific capacity is 0.1A g-1The specific capacity under the current density is as high as 300.3mAh g-1And at 10A g-1Can still maintain 205.1mAh g under the high current density-1. FIG. 9 is a graph showing the relationship between power density and energy density of a lithium ion capacitor assembled by using mixed-phase niobium titanium oxide prepared in example 4 as a negative electrode, and it can be seen that the assembled lithium ion capacitor is 200W kg-1The energy density at the power density is up to 149.6Wh kg-1And the excellent energy storage characteristics are proved again.
The present invention is not limited to the above exemplary embodiments, and any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
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