CN114249351B - Tetragonal niobium pentoxide material and synthesis and application thereof - Google Patents

Tetragonal niobium pentoxide material and synthesis and application thereof Download PDF

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CN114249351B
CN114249351B CN202110325050.7A CN202110325050A CN114249351B CN 114249351 B CN114249351 B CN 114249351B CN 202110325050 A CN202110325050 A CN 202110325050A CN 114249351 B CN114249351 B CN 114249351B
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niobium oxide
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ethanol
tetragonal
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CN114249351A (en
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张洪章
李先锋
丁会彬
张华民
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Dalian Institute of Chemical Physics of CAS
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    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G33/00—Compounds of niobium
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    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • 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
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    • 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
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    • 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
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • 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
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    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to the field of lithium ion battery cathode materials, in particular to synthesis and application of a tetragonal niobium pentoxide material, which comprises the following steps of 1) coating a silicon dioxide layer on the outer surface of raw material powder by taking one or a mixture of two or a mixture of three of amorphous niobium oxide, pseudo-hexagonal niobium oxide and orthogonal niobium oxide as a raw material to obtain a raw material coated with the silicon dioxide layer; 2) Calcining the raw material coated with the silicon dioxide layer at 950-1100 ℃ for 3-8h; soaking calcined powder in 1-4mol L ‑1 The solution of sodium hydroxide (NaOH) for 12 to 48 hours, then solid-liquid separation, washing and drying are carried out to obtain the tetragonal niobium oxide M-Nb 2 O 5 . Synthesized M-Nb 2 O 5 Has a weight of 300mAh g ‑1 The specific capacity and the excellent rate performance of the composite material; the material has intrinsic high lithium ion diffusion capacity, and ensures the ultrahigh-rate charge-discharge capacity and long-cycle stability of the material.

Description

Tetragonal niobium pentoxide material and synthesis and application thereof
Technical Field
The invention relates to the field of lithium ion battery cathode materials, in particular to synthesis and application of a tetragonal-phase niobium pentoxide material.
Background
As for the negative electrode material of the lithium ion battery, the graphite negative electrode is the most common negative electrode material of the current commercial lithium ion battery, the theoretical specific capacity of the graphite negative electrode is 372mAh/g, and the graphite negative electrode has low lithium intercalation potential (<0.2V，vs.Li + /Li). However, at high current densities, the graphite negative electrode has an increased lithium intercalation overpotential, which may cause lithium precipitation and may cause a battery circuit to cause a battery safety problem, and thus it is not suitable for high-rate charge and discharge. Lithium titanate (Li) 4 Ti 5 O 12 LTO) negative electrode lithium intercalation potential is 1.55V (vs. Li) + Li), the volume of the material is reduced in the charging and discharging process, and the material is a negative electrode material which has high safety and long service life and can be charged and discharged quickly. However, due to its high potential and low specific capacity (175 mAh/g), its energy density is difficult to meet the demand for high specific energy batteries. The silicon-based composite negative electrode material is a novel high-specific-capacity negative electrode, the actual specific capacity of the silicon-based composite negative electrode material can reach 600-2000mAh/g, and good high-rate charge and discharge performance can be realized through nanocrystallization of the material. However, the inherent huge volume expansion of the material in the lithium intercalation process affects the cycle life of the material, and the problems of low coulomb charge and discharge for the first time, complex material manufacturing process and the like exist, which make the large-scale practical application of the silicon-based negative electrode difficult to realize. Therefore, exploring a suitable negative electrode material is a hotspot and difficulty in developing the next generation of high-rate and high-safety energy storage technology. Near toMore recently, niobium pentoxide (Nb) 2 O 5 ) Due to the considerable theoretical capacity (200 mAh/g) and the unique crystal structure, the lithium ion ultra-high-speed storage kinetics can be realized, and the lithium ion lithium cathode material is considered to be a promising cathode material. Nb depending on the calcination conditions, precursor and synthesis method 2 O 5 There are many crystal phases, such as TT-, T-, B-, N-, P-, M-and H-Nb 2 O 5 They have different effects on their lithium storage properties. The most common of which are the crystalline phases T, M and H-Nb 2 O 5 Is Nb determined by Brauer et al based on stable thermodynamic states of low, medium and high temperature 2 O 5 Three crystal phases of (2). Orthogonal phase T-Nb 2 O 5 It has received the greatest attention due to its low variation in intercalation structure (no phase change), and high rate capability, but it still has a practical specific capacity of less than 200 mAh/g. Monoclinic phase H-Nb 2 O 5 Has a Li content of up to 250mAh/g (1.0-3.0V vs Li) + /Li). Tetragonal phase M-Nb 2 O 5 Has the characteristics similar to H-Nb 2 O 5 The specific capacity and the rate capability are more excellent. But due to M-Nb 2 O 5 The synthesis conditions are very harsh, and the synthesis is often performed with T-Nb 2 O 5 Or H-Nb 2 O 5 Mixed phases of (2).
Disclosure of Invention
Based on the existing M-Nb 2 O 5 Has the problems of strict synthesis conditions and the like, and the invention provides tetragonal niobium pentoxide (M-Nb) 2 O 5 ) The composite material can be used as a negative electrode for lithium ion batteries and lithium ion capacitors.
The invention provides a tetragonal phase M-Nb 2 O 5 The Nb is changed by the silicon dioxide coating layer 2 O 5 The phase transition temperature and time at high temperature can obtain pure tetragonal phase M-Nb under wider synthesis conditions 2 O 5 Solves the problem of pure phase tetragonal phase M-Nb 2 O 5 The problem of difficult synthesis; synthesized M-Nb 2 O 5 Has a g of 300mAh -1 Has a specific capacity and excellent cycle performanceAnd ultrahigh multiplying power charge-discharge capacity; the material has intrinsic high lithium ion diffusion capability.
The invention provides a complete technical scheme, a method for synthesizing tetragonal niobium oxide,
1) Taking one or a mixture of two or a mixture of three of amorphous niobium oxide, pseudo-hexagonal niobium oxide and orthorhombic niobium oxide as a raw material, and coating a silicon dioxide layer on the outer surface of the raw material powder to obtain a raw material coated with the silicon dioxide layer;
2) Calcining the raw material coated with the silica layer at 950-1100 deg.C (preferably 1050-1100 deg.C) for 3-8h (preferably 4-6h, more preferably 5 h); soaking the calcined powder in 1-4mol L -1 (preferably 2mol L) -1 -3mol L -1 More preferably 3mol L -1 ) Is added into sodium hydroxide (NaOH) solution for 12 to 48 hours (preferably 20 to 30 hours, more preferably 24 hours), then solid-liquid separation, washing and drying are carried out to obtain tetragonal niobium oxide M-Nb 2 O 5 。
The process of wrapping the outer surface of the raw material in the step 1) with the silicon dioxide layer is as follows: adding one or two or three mixture powders of amorphous niobium oxide, pseudo hexagonal niobium oxide and orthorhombic niobium oxide as raw materials into a mixed powder with the volume ratio of 4-8:2 (preferably 5-7): 70 (preferably 0.1 to 0.2; and (2) weighing hexadecyl trimethyl ammonium bromide (CTAB), adding into the suspension, and uniformly stirring, wherein the mass ratio of CTAB to the raw materials is 1:5-20 (preferably 1; then adding the mixture into an ethanol water solution in a volume ratio of 1-3:70 (preferably 1-2, more preferably 1; finally, the concentration is 0.001-0.05g ml -1 (preferably 0.008-0.015 g/ml) -1 ) Dropwise adding an ethanol solution of Tetraethoxysilane (TEOS) into the solution, wherein the volume ratio of the tetraethoxysilane ethanol solution to the ethanol aqueous solution is 1.
A. The amorphous niobium oxide is synthesized by a hydrothermal method: reacting NbCl 5 Powder is added intoIn benzyl alcohol; keeping the temperature at 180-220 ℃ for 12-48 hours, carrying out solid-liquid separation, and drying the solid to obtain amorphous niobium oxide; nbCl 5 A mass (g) to volume (ml) ratio to benzyl alcohol of 0.1 to 0.5 (preferably 0.2 to 0.3;
or B, preparing one or two mixtures or three mixtures of amorphous niobium oxide, pseudo hexagonal niobium oxide and orthorhombic niobium oxide: and B, calcining the amorphous niobium oxide obtained in the step A at 300-700 ℃ for 2-5 hours to obtain one or two or three of amorphous niobium oxide, pseudo hexagonal niobium oxide and orthorhombic niobium oxide, which is called low-temperature calcined niobium oxide.
Tetragonal niobium oxide synthesized by the above synthesis method.
The tetragonal niobium oxide is used as a negative electrode active material in a lithium ion battery or a lithium ion capacitor.
The invention has the beneficial effects that:
the invention provides a tetragonal phase M-Nb 2 O 5 By changing Nb through a silicon dioxide coating layer 2 O 5 The phase transition temperature and time at high temperature can obtain pure tetragonal phase M-Nb under wider synthesis conditions 2 O 5 Solves the problem of pure tetragonal phase M-Nb 2 O 5 The problem of difficult synthesis; synthesized M-Nb 2 O 5 Has a g of 300mAh -1 The specific capacity and the excellent rate performance of the composite material are achieved; the material has intrinsic high lithium ion diffusion capacity, and ensures the ultrahigh-rate charge-discharge capacity and long-cycle stability of the material.
Drawings
FIG. 1 shows M-Nb obtained in example 1 2 O 5 Schematic synthesis of sample material A2;
FIG. 2 is an XRD diffraction curve and standard characteristic peaks of sample A2 obtained in example 1;
FIG. 3 is an XRD phase characterization of sample materials A7-A9 of comparative examples 1-3;
FIG. 4 shows M-Nb obtained in example 1 2 O 5 Diffusion coefficient calculated for sample material A2 half cell GITT;
FIG. 5 shows M-Nb obtained in example 1 2 O 5 Sample material A2 half-cell charge-discharge curve;
FIG. 6 shows M-Nb obtained in example 1 2 O 5 Testing the cycle performance of the sample material A2 half cell;
FIG. 7 shows M-Nb obtained in example 1 2 O 5 Testing the rate capability of a sample material A2 half cell;
FIG. 8 shows M-Nb obtained in example 1 2 O 5 TEM topography before (left) and after (right) washing with NaOH.
Detailed Description
Example 1
Preparing raw materials:
0.243g of milled NbCl 5 The powder was added to 18mL of benzyl alcohol. The resulting solution was transferred to a 22 ml teflon liner and then placed in an autoclave. The autoclave was placed at a constant temperature of 180 ℃ for 24 hours and then air-cooled to room temperature. The solid was collected by centrifugation, washed with ethanol and dried at 50 ℃ to give starting material A1.
Synthesis of sample material:
calcining the raw material A1 at 700 ℃ for 2h to obtain T-Nb 2 O 5 The preparation steps of the (orthorhombic niobium pentoxide) are shown in figure 1; 0.1g of calcined material is added into a solution containing 50ml of ethanol and 20ml of deionized water, and ultrasonic treatment is carried out for 10min to form a suspension with good dispersibility. 0.02g of cetyltrimethylammonium bromide (CTAB) was weighed into the above suspension and stirred for 5 minutes. Then, 1ml of concentrated aqueous ammonia (mass fraction 28%) was added and stirred for 5 minutes. Finally, the mixture will contain 0.012g ml -1 10ml of ethyl silicate (TEOS) ethanol solution is slowly added into the suspension dropwise, and after 12 hours of stirring, the suspension is centrifuged, the solid is washed, and dried at 50 ℃.
The dried powder was calcined at 1050 ℃ for 5h. Placing the calcined powder in a concentration of 3mol L -1 50ml of sodium hydroxide (NaOH) solution and standing for 24 hours, then centrifuging, washing with solid deionized water and drying to obtain pure phase M-Nb 2 O 5 (A2) .1. The It can be seen from FIG. 2 that it is a pure phase M-Nb 2 O 5 The purity is more than 99 percent, and the rest is T-Nb 2 O 5 And H-Nb 2 O 5 。
Preparing a half cell:
preparing an electrode by using the sample material (A2) as an electrode active substance; the material composition of the electrode is as follows: the mass ratio of the electrode material (A2), the carbon black and the PVDF is 8.
The GITT technique of FIG. 4 shows an ion diffusion coefficient of 10 -10 -10 -9 In the middle of; FIG. 5 shows that the reversible capacity reaches 300mAh g -1 (ii) a FIG. 6 shows that it is at 2 ag -1 The following has good cycle performance, and fig. 7 shows that it has 20C ultra high rate performance. As can be seen in fig. 8, the surface silica layer was removed after soaking in the sodium hydroxide solution, and a pure-phase niobium pentoxide material was obtained.
Example 2
The starting material used in example 2 was the starting material A1 prepared in example 1
Synthesis of sample material:
calcining the raw material A1 at 700 ℃ for 2h to obtain T-Nb 2 O 5 (orthogonal niobium pentoxide), 0.1g of the calcined material is added into a solution containing 50ml of ethanol and 20ml of deionized water, and ultrasonic treatment is carried out for 10min to form a suspension with good dispersibility. 0.02g of cetyltrimethylammonium bromide (CTAB) was weighed into the above suspension and stirred for 5 minutes. Subsequently, 1ml of concentrated aqueous ammonia (28% by mass) was added and stirred for 5 minutes. Finally, the mixture will contain 0.008gml -1 10ml of ethyl silicate (TEOS) ethanol solution is slowly dripped into the suspension, stirred for 12 hours, centrifuged, washed and dried at 50 ℃. The dried powder was calcined at 950 ℃ for 5h. Placing the calcined powder in a concentration of 3mol L -1 50ml of sodium hydroxide (NaOH) solution and standing for 24 hours, then centrifuging, washing by deionized water and drying to obtain pure phase M-Nb 2 O 5 (A3)。
Preparing a half cell:
from Nb 2 O 5 The material (A3) acts as electricityThe electrode active material was used to prepare a half cell, and the preparation procedure and conditions were the same as in example 1.
The obtained A3 is pure phase M-Nb 2 O 5 The purity is more than 95 percent, and the rest is T-Nb 2 O 5 (ii) a The capacity can reach 295mAh g -1 Has stable cycle performance and ultrahigh rate performance.
Example 3
The starting material used in example 3 was the starting material A1 prepared in example 1
Synthesis of sample material:
calcining the raw material A1 at 700 ℃ for 2h to obtain T-Nb 2 O 5 0.1g of calcined material is taken and added into a solution containing 50ml of ethanol and 20ml of deionized water, and the mixture is subjected to ultrasonic treatment for 10min to form a suspension with good dispersibility. 0.02g of cetyltrimethylammonium bromide (CTAB) was weighed into the above suspension and stirred for 5 minutes. Subsequently, 1ml of concentrated aqueous ammonia (28% by mass) was added and stirred for 5 minutes. Finally, the mixture will contain 0.01g ml -1 10ml of ethyl silicate (TEOS) ethanol solution is slowly dripped into the suspension, stirred for 12 hours, centrifuged, washed and dried at 50 ℃. The dried powder was calcined at 1000 ℃ for 5h. Placing the calcined powder in a concentration of 3mol L -1 50ml of sodium hydroxide (NaOH) solution and standing for 24 hours, then centrifuging, washing by deionized water and drying to obtain pure phase M-Nb 2 O 5 (A4) .1. The Preparing a half cell:
from Nb 2 O 5 The material (A4) was used as an electrode active material to prepare a half cell, and the preparation procedure and conditions were the same as in example 1.
The obtained A4 is pure phase M-Nb 2 O 5 The purity is more than 99 percent, and the rest is T-Nb 2 O 5 And H-Nb 2 O 5 (ii) a The capacity can reach 300mAh g -1 Has stable cycle performance and ultrahigh rate performance.
Example 4
The starting material used in example 4 was the starting material A1 prepared in example 1
Synthesis of sample material:
calcining the raw material A1 at 700 ℃ for 2h to obtainTo T-Nb 2 O 5 0.1g of calcined material is taken and added into a solution containing 50ml of ethanol and 20ml of deionized water, and the mixture is subjected to ultrasonic treatment for 10min to form a suspension with good dispersibility. 0.02g of cetyltrimethylammonium bromide (CTAB) was weighed into the above suspension and stirred for 5 minutes. Then, 1ml of concentrated aqueous ammonia (mass fraction 28%) was added and stirred for 5 minutes. Finally, the solution will contain 0.015g ml -1 10ml of ethyl silicate (TEOS) ethanol solution is slowly dripped into the suspension, stirred for 12 hours, centrifuged, washed and dried at 50 ℃. The dried powder was calcined at 1100 ℃ for 5h. Placing the calcined powder in a concentration of 3mol L -1 50ml of sodium hydroxide (NaOH) solution and standing for 24 hours, then centrifuging, washing by deionized water and drying to obtain pure phase M-Nb 2 O 5 (A5)。
From Nb 2 O 5 The material (A5) was used as an electrode active material to prepare a half cell, and the preparation procedure and conditions were the same as in example 1.
The obtained A5 is pure phase M-Nb 2 O 5 The purity is more than 99 percent, and the rest is H-Nb 2 O 5 (ii) a The capacity can reach 300mAh g -1 Has stable cycle performance and ultrahigh rate performance.
Example 5
The starting material used in example 5 was the starting material A1 prepared in example 1
Synthesis of sample material:
taking 0.1g of the raw material A, adding the raw material A into a solution containing 50ml of ethanol and 20ml of deionized water, and carrying out ultrasonic treatment for 10min to form a suspension with good dispersibility. 0.02g of cetyltrimethylammonium bromide (CTAB) was weighed into the above suspension and stirred for 5 minutes. Then, 1ml of concentrated aqueous ammonia (mass fraction 28%) was added and stirred for 5 minutes. Finally, the solution will contain 0.012g ml -1 10ml of ethyl silicate (TEOS) ethanol solution is slowly dripped into the suspension, stirred for 12 hours, centrifuged, washed and dried at 50 ℃. The dried powder was calcined at 1050 ℃ for 5h. Placing the calcined powder in a concentration of 3mol L -1 50ml of sodium hydroxide (NaOH) solution and standing for 24 hours, then centrifuging, washing by deionized water and drying to obtain pure phase M-Nb 2 O 5 (A6)。
From Nb 2 O 5 The material (A6) was used as an electrode active material to prepare a half cell, and the preparation procedure and conditions were the same as in example 1.
The obtained A6 is pure phase M-Nb 2 O 5 The purity is more than 99 percent, and the rest is T-Nb 2 O 5 And H-Nb 2 O 5 (ii) a The capacity can reach 300mAh g -1 Has stable cycle performance and ultrahigh rate performance.
Example 6
The starting material used in example 6 was the starting material A1 prepared in example 1
Synthesis of sample material:
calcining the raw material A1 at 700 ℃ for 2h to obtain T-Nb 2 O 5 The preparation steps of the (orthorhombic niobium pentoxide) are shown in figure 1; 0.1g of the calcined material is added into a solution containing 50ml of ethanol and 20ml of deionized water, and the mixture is subjected to ultrasonic treatment for 10min to form a suspension with good dispersibility. 0.02g of cetyltrimethylammonium bromide (CTAB) was weighed into the above suspension and stirred for 5 minutes. Then, 1ml of concentrated aqueous ammonia (mass fraction 28%) was added and stirred for 5 minutes. Finally, the solution will contain 0.001g ml -1 10ml of ethyl silicate (TEOS) ethanol solution is slowly added into the suspension dropwise, and after 12 hours of stirring, the suspension is centrifuged, the solid is washed, and dried at 50 ℃.
The dried powder was calcined at 1050 ℃ for 5h. Placing the calcined powder in a concentration of 3mol L -1 50ml of sodium hydroxide (NaOH) solution and standing for 24 hours, then centrifuging, washing with solid deionized water and drying to obtain pure phase M-Nb 2 O 5 (A7)。
Preparing a half cell:
from Nb 2 O 5 The material (A7) was used as an electrode active material to prepare a half cell, and the preparation procedure and conditions were the same as in example 1.
The obtained A7 is pure phase M-Nb 2 O 5 The purity is more than 95 percent, and the rest is H-Nb 2 O 5 (ii) a The capacity can reach 295mAh g -1 Has stable cycle performance and ultrahigh rate performance.
Selected in comparison with example 1The ethyl silicate (TEOS) concentration is lower, which is the lower limit of experimental conditions, so that the formed SiO 2 The coating layer is thin, the effect is slightly poor, and H-Nb is more easily generated when the coating layer is calcined at the same temperature 2 O 5 I.e. H-Nb in the product 2 O 5 Relatively much.
Example 7
The starting material used in example 7 was the starting material A1 prepared in example 1
Synthesis of sample material:
calcining the raw material A1 at 700 ℃ for 2h to obtain T-Nb 2 O 5 The preparation steps of the (orthorhombic niobium pentoxide) are shown in figure 1; 0.1g of calcined material is added into a solution containing 50ml of ethanol and 20ml of deionized water, and ultrasonic treatment is carried out for 10min to form a suspension with good dispersibility. 0.02g of cetyltrimethylammonium bromide (CTAB) was weighed into the above suspension and stirred for 5 minutes. Subsequently, 1ml of concentrated aqueous ammonia (28% by mass) was added and stirred for 5 minutes. Finally, the solution will contain 0.05g ml -1 10ml of ethyl silicate (TEOS) ethanol solution is slowly added into the suspension dropwise, and after 12 hours of stirring, the suspension is centrifuged, the solid is washed, and dried at 50 ℃.
The dried powder was calcined at 1050 ℃ for 5h. Placing the calcined powder in a concentration of 3mol L -1 50ml of sodium hydroxide (NaOH) solution and standing for 24 hours, then centrifuging, washing with solid deionized water and drying to obtain pure phase M-Nb 2 O 5 (A8)。
Preparing a half cell:
from Nb 2 O 5 The material (A8) was used as an electrode active material to prepare a half cell, and the preparation procedure and conditions were the same as in example 1.
The obtained A8 is pure phase M-Nb 2 O 5 The purity is more than 95 percent, and the rest is T-Nb 2 O 5 (ii) a The capacity can reach 295mAh g -1 Has stable cycle performance and ultrahigh rate performance.
The ethyl silicate (TEOS) concentration was chosen to be higher than in example 1, as the upper limit of the experimental conditions, so that SiO is formed 2 Thick coating layer, tetragonal phase M-Nb synthesized at 1050 DEG C 2 O 5 Crystals of (2)The degree is slightly worse.
Comparative example 1
The starting material used in comparative example 1 was the starting material A1 prepared in example 1
Synthesis of sample material:
heating the raw material A1 to 800 ℃ from room temperature at a heating rate of 5 ℃/min in an Air (Air) atmosphere; keeping the temperature for heat treatment for 2h, and then cooling to room temperature at the speed of 10 ℃/min to obtain T-Nb 2 O 5 And M-Nb 2 O 5 Mixed phase (A9).
From Nb 2 O 5 The material (A9) was used as an electrode active material to prepare a half cell, and the preparation procedure and conditions were the same as in example 1.
As can be seen from the XRD results of FIG. 3, the obtained A9 is T-Nb 2 O 5 And M-Nb 2 O 5 Mixed phase, the molar ratio of the two contents is about 0.8:0.2; the mixed phase ratio capacity is 230mAh g -1 Has poor circulation stability and rate capability, and has only 50mAhg at 20C rate -1 The specific capacity of (a).
Comparative example 2
The starting material used in comparative example 2 was the starting material A1 prepared in example 1
Synthesis of sample material:
heating the raw material A1 to 850 ℃ from room temperature at a heating rate of 5 ℃/min in an Air (Air) atmosphere; keeping the temperature for heat treatment for 2H, and then cooling to room temperature at the speed of 10 ℃/min to obtain H-Nb 2 O 5 And M-Nb 2 O 5 Mixed phase (A10).
From Nb 2 O 5 The material (a 10) was used as an electrode active material to prepare a half cell, and the preparation procedure and conditions were the same as in example 1.
As can be seen from the XRD results of FIG. 3, the obtained A10 is M-Nb 2 O 5 And H-Nb 2 O 5 Mixed phase, the molar ratio of the two contents is about 0.6:0.4 of the total weight of the mixture; the mixed phase ratio capacity is 250mAh g -1 Has poor circulation stability and rate capability, and has only 60mAhg at 20C rate -1 The specific capacity of (A).
Comparative example 3
The starting material used in comparative example 3 was the starting material A1 prepared in example 1
Synthesis of sample material:
heating the raw material A1 to 900 ℃ from room temperature at a heating rate of 5 ℃/min in an Air (Air) atmosphere; keeping the temperature for heat treatment for 2H, and then cooling to room temperature at the speed of 10 ℃/min to obtain H-Nb 2 O 5 (A11)。
From Nb 2 O 5 The material (a 11) was used as an electrode active material to prepare a half cell, and the preparation procedure and conditions were the same as in example 1.
As can be seen from the XRD results of FIG. 3, the obtained A11 is H-Nb 2 O 5 And M-Nb 2 O 5 Mixed phase, the molar ratio of the two contents is about 0.8:0.2; the mixed phase ratio capacity is 250mAh g -1 Has poor circulation stability and rate capability, and has only 60mAhg at 20C rate -1 The specific capacity of (a).
Comparative example 4
The starting material used in comparative example 4 was the starting material A1 prepared in example 1
Calcining the raw material A1 at 700 ℃ for 2h to obtain T-Nb 2 O 5 0.1g of calcined material is added into a solution containing 50ml of ethanol and 20ml of deionized water, and ultrasonic treatment is carried out for 10min to form a suspension with good dispersibility. 0.02g of cetyltrimethylammonium bromide (CTAB) was weighed into the above suspension and stirred for 5 minutes. Then, 1ml of concentrated aqueous ammonia (mass fraction 28%) was added and stirred for 5 minutes. Finally, the solution will contain 0.0008g ml -1 10ml of ethyl silicate (TEOS) ethanol solution is slowly dripped into the suspension, stirred for 12 hours, centrifuged, washed and dried at 50 ℃. The dried powder was calcined at 1000 ℃ for 5h. Placing the calcined powder in a concentration of 3mol L -1 50ml of sodium hydroxide (NaOH) solution and standing for 24 hours, then centrifuging, washing by deionized water and drying to obtain H-Nb 2 O 5 And M-Nb 2 O 5 Mixed phase (a 12) in a molar ratio of about 0.4:0.6.
with mixed phases of Nb 2 O 5 Preparation of semielectricity by using material as electrode active substanceThe cell, preparation procedure and conditions were the same as in example 1.
The resulting mixed phase Nb 2 O 5 A12 specific capacity 270mAh g -1 Has poor circulation stability and rate capability, and has only 60mAhg at 20C rate -1 The specific capacity of (A).
Comparative example 5
The starting material used in comparative example 5 was the starting material A1 prepared in example 1
Synthesis of sample material:
calcining the raw material A1 at 700 ℃ for 2h to obtain T-Nb 2 O 5 0.1g of calcined material is taken and added into a solution containing 50ml of ethanol and 20ml of deionized water, and the mixture is subjected to ultrasonic treatment for 10min to form a suspension with good dispersibility. 0.02g of cetyltrimethylammonium bromide (CTAB) was weighed into the above suspension and stirred for 5 minutes. Subsequently, 1ml of concentrated aqueous ammonia (28% by mass) was added and stirred for 5 minutes. Finally, the mixture will contain 0.015g ml -1 10ml of ethyl silicate (TEOS) ethanol solution is slowly dripped into the suspension, stirred for 12 hours, centrifuged, washed and dried at 50 ℃. The dried powder was calcined at 800 ℃ for 5h. Placing the calcined powder in a concentration of 3mol L -1 50ml of sodium hydroxide (NaOH) solution and standing for 24 hours, then centrifuging, washing by deionized water and drying to obtain T-Nb 2 O 5 And M-Nb 2 O 5 Mixed phase (a 13) in a molar ratio of about 0.5:0.5..
With mixed phases of Nb 2 O 5 Materials as electrode active materials half cells were prepared using the same procedure and conditions as in example 1.
The resulting mixed phase Nb 2 O 5 Its capacity is 220mAh g -1 Has poor circulation stability and rate capability, and only 50mAhg at 20C rate -1 The specific capacity of (A). Comparative examples 1 to 5 are niobium pentoxide materials obtained by direct calcination without silica coating, and by adjusting the calcination temperature, when the direct calcination temperature is below 900 ℃, the XRD patterns show that tetragonal M-Nb is obtained by synthesis 2 O 5 But also includes other crystalline phases, with very low purity. When the temperature is raised above 900 c,it is seen by XRD pattern that pure phase H-Nb is obtained 2 O 5 A material.
The niobium pentoxide material obtained by calcining after being coated by silicon dioxide is subjected to regulation and control of preparation parameters and conditions to obtain the tetragonal phase M-Nb with the purity of more than 90 percent 2 O 5 The material is calcined at 950-1100 deg.c after coating silica layer, unlike the case of calcining without coating silica layer, and high purity tetragonal phase M-Nb can be obtained 2 O 5 The specific capacity of the material can reach 300Ah g when the material is used for lithium ion battery electrodes -1 And the excellent cycle performance and rate performance are shown.
Although the present invention has been described with reference to a few preferred embodiments, it should be understood that various changes and modifications can be made without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (7)

1. A synthetic method of tetragonal niobium oxide is characterized in that:
1) Taking one or a mixture of two or a mixture of three of amorphous niobium oxide, pseudo-hexagonal niobium oxide and orthorhombic niobium oxide as a raw material, and coating a silicon dioxide layer on the outer surface of the raw material powder to obtain a raw material coated with the silicon dioxide layer;
2) Calcining the raw material coated with the silicon dioxide layer at 1050-1100 ℃ for 3-8h; soaking the calcined powder in 1-4mol L -1 The sodium hydroxide solution is added for 12 to 48 hours, and then the tetragonal niobium oxide M-Nb is obtained by solid-liquid separation, washing and drying 2 O 5 ；
The process of wrapping the outer surface of the raw material in the step 1) with the silicon dioxide layer is as follows: adding one or two or three mixture powders of amorphous niobium oxide, pseudo hexagonal niobium oxide and orthorhombic niobium oxide as raw materials into ethanol and water in a volume ratio of 4-8:2 in the presence of a water solution of a solvent,forming a suspension, wherein the mass g/volume ml ratio of the raw material to the ethanol aqueous solution is 0.05-1:70; and weighing hexadecyl trimethyl ammonium bromide, adding the hexadecyl trimethyl ammonium bromide into the suspension, and uniformly stirring, wherein the mass ratio of the hexadecyl trimethyl ammonium bromide to the raw materials is 1:5-20; then adding 25-28% ammonia water by mass and uniformly stirring, wherein the volume ratio of the ammonia water to the ethanol water solution is 1-3:70; finally, the concentration is 0.001-0.05g ml -1 And (3) dropwise adding an ethyl orthosilicate ethanol solution into the solution, wherein the volume ratio of the ethyl orthosilicate ethanol solution to the ethanol aqueous solution is 1.
2. A method of synthesis according to claim 1, characterized in that:
the process of wrapping the silicon dioxide layer on the outer surface of the raw material comprises the following steps: adding one or a mixture of two or a mixture of three of amorphous niobium oxide, pseudo-hexagonal niobium oxide and orthorhombic niobium oxide which are used as raw materials into ethanol and water in a volume ratio of 5-7:2, forming a suspension, wherein the mass g/volume ml ratio of the raw material to the ethanol aqueous solution is 0.1-0.2:70; and weighing hexadecyl trimethyl ammonium bromide, adding the hexadecyl trimethyl ammonium bromide into the suspension, and uniformly stirring, wherein the mass ratio of the hexadecyl trimethyl ammonium bromide to the raw materials is 1:10-15 parts of; then adding 25-28% ammonia water by mass and uniformly stirring, wherein the volume ratio of the ammonia water to the ethanol water solution is 1-2:70; finally, the concentration is 0.008 to 0.015g ml -1 And (3) dropwise adding an ethanol solution of the ethyl orthosilicate into the solution, wherein the volume ratio of the ethanol solution of the ethyl orthosilicate to the ethanol aqueous solution is 1.
3. A method of synthesis according to claim 1, characterized in that: calcining the raw material coated with the silicon dioxide layer at 1050-1100 ℃ for 4-6h; soaking the calcined powder in 2mol L solution -1 -3mol L -1 Then the solution is subjected to solid-liquid separation, washing and drying to obtain tetragonal niobium oxide M-Nb 2 O 5 。
4. A method of synthesis according to claim 1, characterized in that:
A. the amorphous niobium oxide is synthesized by a hydrothermal method: reacting NbCl 5 Adding the powder into benzyl alcohol; at a temperature of 180 deg.C o C – 220 o Keeping the temperature at the temperature of C for 12-48 hours, carrying out solid-liquid separation, and drying the solid to obtain amorphous niobium oxide; nbCl 5 The mass g/volume ml ratio of the benzyl alcohol to the benzyl alcohol is 0.1-0.5;
or B, preparing one or two mixtures or three mixtures of amorphous niobium oxide, pseudo hexagonal niobium oxide and orthorhombic niobium oxide: and B, calcining the amorphous niobium oxide obtained in the step A at 300-700 ℃ for 2-5 hours to obtain one or two or three of amorphous niobium oxide, pseudo hexagonal niobium oxide and orthorhombic niobium oxide, which is called low-temperature calcined niobium oxide.
5. The method of synthesis according to claim 4, wherein: nbCl in amorphous niobium oxide hydrothermal synthesis process 5 The mass g/volume ml ratio of the benzyl alcohol to the benzyl alcohol is 0.2-0.3: 18.
6. A tetragonal niobium oxide synthesized according to the synthesis method of any one of claims 1 to 5.
7. Use of the tetragonal niobium oxide of claim 6 as a negative electrode active material in a lithium ion battery or a lithium ion capacitor.
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