CN115799486A - Micron-sized lithium titanate and multi-walled carbon nanotube composite material and preparation method and application thereof - Google Patents
Micron-sized lithium titanate and multi-walled carbon nanotube composite material and preparation method and application thereof Download PDFInfo
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 239000002048 multi walled nanotube Substances 0.000 title claims abstract description 99
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 98
- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
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- 239000006185 dispersion Substances 0.000 claims description 27
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 13
- 229910017604 nitric acid Inorganic materials 0.000 claims description 13
- 239000004094 surface-active agent Substances 0.000 claims description 13
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 11
- 238000000137 annealing Methods 0.000 claims description 11
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 11
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- 238000001914 filtration Methods 0.000 claims description 10
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- 239000007787 solid Substances 0.000 claims description 9
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- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- -1 octadecyl dimethyl benzyl quaternary ammonium chloride Chemical compound 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 3
- JBIROUFYLSSYDX-UHFFFAOYSA-M benzododecinium chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 JBIROUFYLSSYDX-UHFFFAOYSA-M 0.000 claims description 3
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- 230000000694 effects Effects 0.000 description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
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- 230000000052 comparative effect Effects 0.000 description 8
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- 238000001132 ultrasonic dispersion Methods 0.000 description 6
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
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- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000001453 impedance spectrum Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 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 description 2
- 238000001354 calcination Methods 0.000 description 2
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- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
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- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 1
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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- 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
Abstract
The invention belongs to the technical field of electrochemical energy storage, and particularly relates to a micron-sized lithium titanate and multi-walled carbon nanotube composite material as well as a preparation method and application thereof. The invention discloses a micron-sized lithium titanate and multi-walled carbon nanotube composite material, wherein the micron-sized lithium titanate is micron-sized spherical particles and is formed by cross stacking of nanoscale sheets, and multi-walled carbon nanotubes are distributed on the surface of the micron-sized lithium titanate. The micron-sized lithium titanate with the hierarchical structure has the high specific capacity and high power performance of a nano material, the high tap density of a micron-sized material and the adaptability of industrial preparation, the multi-walled carbon nanotube has excellent conductivity, the problem of poor conductivity of lithium titanate is solved, and the multi-walled carbon nanotube can effectively improve the performance of a secondary battery when being used as an electrode material.
Description
Technical Field
The invention belongs to the technical field of electrochemical energy storage, and particularly relates to a micron-sized lithium titanate and multi-walled carbon nanotube composite material as well as a preparation method and application thereof.
Background
Electrochemical energy storage technologies represented by secondary batteries are widely applied to the fields of large-scale energy storage, electric vehicles, consumer electronics and the like, and in recent years, with the increasing emphasis on carbon emission, the demand and performance requirements of people on the number of secondary batteries are explosively increased. The performance of the electrode material in the secondary battery directly determines the energy density, cycle life and rate performance of the battery, and the correspondence to the electrode material means that the electrode material needs a large number of cation storage sites, strong structural stability and excellent conductivity.
The lithium titanate material has excellent structural stability and abundant cation storage sites, so that the lithium titanate material has longer cycle life and higher theoretical specific capacity. However, lithium titanate is a semiconductor, and has weak electron conductivity, so that solid-phase migration of cations is limited, and the actual specific capacity is low. Therefore, how to improve the actual specific capacity of the lithium titanate battery becomes a problem to be solved urgently at the present stage.
Disclosure of Invention
The present invention is based on the discovery and recognition by the inventors of the following facts and problems:
the prior art mostly discloses a technical route for nano-crystallization of lithium titanate materials, which can shorten a cation migration path and improve specific capacity. However, the nano technology has high cost, and the nano material has low tap density in the practical application process, so that the requirements of industrial production cannot be met. In other techniques, carbon obtained by pyrolysis and graphitization is coated on the surface of lithium carbonate, or a hydrothermal reaction is used for preparing the carbon-containing lithium titanate. However, the carbon materials formed by the methods are generally low in graphitization degree, poor in electric conduction effect and not worthy of actual industrial production.
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, the invention provides a micron-sized lithium titanate and multi-walled carbon nanotube composite material, wherein the micron-sized lithium titanate is formed by cross stacking of nanoscale sheets, the micron-sized lithium titanate with a hierarchical structure simultaneously has the high specific capacity and high rate capability of a nanoscale material, the high tap density of a micron-sized material and the adaptability of industrial preparation, and the multi-walled carbon nanotube has excellent conductivity and makes up the problem of poor conductivity of lithium titanate, so that the composite material not only has the high specific capacity and high rate capability, but also has a good conductive effect.
According to the micron-sized lithium titanate and multi-walled carbon nanotube composite material disclosed by the embodiment of the invention, the micron-sized lithium titanate is micron-sized spherical particles and is formed by cross stacking of nanoscale sheets, and the multi-walled carbon nanotubes are distributed on the surface of the micron-sized lithium titanate.
The micron-sized lithium titanate and the multi-walled carbon nanotube composite material provided by the embodiment of the invention have the advantages and technical effects that 1, in the embodiment of the invention, the micron-sized lithium titanate with the hierarchical structure not only has the high specific capacity and high rate capability of a nano-sized material, but also has the high tap density of the micron-sized material and the suitability for industrial preparation; 2. in the embodiment of the invention, the multi-walled carbon nano tube with excellent conductivity is adopted to carry out composite modification on the micron-sized lithium titanate, so that the defect that the electron conductivity of the lithium titanate is weaker is overcome, and the composite material not only has high specific capacity and high rate capability, but also has good conductive effect.
In some embodiments, the mass fraction of the multi-walled carbon nanotubes in the composite material is 3 to 10%; and/or the particle size of the micron-sized lithium titanate is 2 to 3 mu m, the thickness of the nanoscale sheet is 5 to 8nm, and the width of the nanoscale sheet is 50 to 500nm.
The embodiment of the invention also provides a preparation method of the micron-sized lithium titanate and multi-walled carbon nanotube composite material, which comprises the following steps:
(1) Adding the multi-walled carbon nanotube into an acid solution for dispersion, heating and refluxing, and filtering to obtain a multi-walled carbon nanotube A;
(2) Adding the multi-walled carbon nanotube A obtained in the step (1) into a surfactant solution to obtain a multi-walled carbon nanotube dispersion liquid B;
(3) Dispersing titanium dioxide in a concentrated alkali solution to perform hydrothermal reaction, dispersing the obtained product in a dilute alkali solution, adding hydrogen peroxide to perform heating reaction, performing acid exchange on the obtained product, and then dispersing in a lithium hydroxide solution to perform hydrothermal reaction to obtain micron-sized lithium titanate;
(4) And (3) dispersing the micron-sized lithium titanate obtained in the step (3) in water to obtain a micron-sized lithium titanate water dispersion, adding the multi-walled carbon nanotube dispersion B obtained in the step (2) into the micron-sized lithium titanate water dispersion, carrying out aging reaction, filtering, and annealing the obtained solid to obtain the composite material.
The preparation method of the embodiment of the invention has the advantages and technical effects that the preparation method of the micron lithium titanate and multi-walled carbon nanotube composite material can improve the dispersion property and the charging property of the multi-walled carbon nanotube in an aqueous solution after the surface modification treatment is carried out on the multi-walled carbon nanotube, so that the multi-walled carbon nanotube and the micron lithium titanate with a hierarchical structure can be compounded through electrostatic interaction, and the multi-walled carbon nanotube and the micron lithium titanate are uniformly compounded; 2. according to the preparation method provided by the embodiment of the invention, titanium dioxide is used as a titanium source to prepare the micron-sized lithium titanate with the hierarchical structure, and the material has dual properties of a nano-sized material and a micron-sized material, and is suitable for application in a battery; 3. the preparation method provided by the embodiment of the invention has the advantages of low energy consumption and simple process, and is suitable for popularization and application of industrial production.
In some embodiments, in the step (1), the ratio of the multi-walled carbon nanotubes to the acid solution is 1 to 2g of the multi-walled carbon nanotubes per 500mL of the acid solution.
In some embodiments, in the step (2), the mass ratio of the surfactant to the multi-wall carbon nanotube A is 1; the surfactant comprises at least one of octadecyl dimethyl benzyl quaternary ammonium chloride, hexadecyl trimethyl quaternary ammonium bromide, hexadecyl trimethyl quaternary ammonium chloride and dodecyl dimethyl benzyl ammonium chloride.
In some embodiments, in the step (3), the temperature of the hydrothermal reaction is 120 to 180 ℃, and the time of the hydrothermal reaction is 12 to 24h; and/or the temperature of the heating reaction is 120 to 150 ℃, and the time of the heating reaction is 6 to 18h.
In some embodiments, in the step (3), the acid exchange uses 0.01-0.02M nitric acid, and the time for acid exchange is not less than 72h.
In some embodiments, in the step (4), the aging reaction time is 12 to 24h; and/or the temperature of the annealing treatment is 350 to 450 ℃, and the time of the annealing treatment is 4 to 8h.
The embodiment of the invention also provides an electrode material which comprises the composite material or the composite material prepared by the method.
The electrode material in the embodiment of the present invention has all the technical characteristics of the micron-sized lithium titanate and the multi-walled carbon nanotube composite material in the embodiment of the present invention, and therefore, has all the advantages and technical effects of the micron-sized lithium titanate and the multi-walled carbon nanotube composite material in the embodiment of the present invention, and are not described herein again.
The embodiment of the invention also provides a magnesium ion battery which comprises the electrode material.
Advantages and technical effects brought by the magnesium ion battery in the embodiment of the present invention, the magnesium ion battery in the embodiment of the present invention has all technical features of the electrode material in the embodiment of the present invention, and therefore, all advantages and technical effects brought by the electrode material in the embodiment of the present invention are provided, and are not described herein again.
Drawings
Fig. 1 is a transmission electron microscope image of a micron-sized lithium titanate/multi-walled carbon nanotube composite material having a hierarchical structure prepared in example 1;
FIG. 2 is a scanning electron microscope image of the micron-sized lithium titanate/multi-walled carbon nanotube composite material having a hierarchical structure prepared in example 1;
FIG. 3 is an impedance spectrum before and after the micron-sized lithium titanate composite multi-walled carbon nanotube in example 1;
FIG. 4 is a graph showing the performance test of the composite material prepared in example 1 when it is used as an electrode material for a magnesium ion secondary battery.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
The embodiment of the invention provides micron-sized lithium titanate and multi-walled carbon nanotubes, wherein the micron-sized lithium titanate is micron-sized spherical particles and is formed by cross stacking of nanoscale sheets, and the multi-walled carbon nanotubes are distributed on the surface of the micron-sized lithium titanate.
According to the micron-sized lithium titanate and multi-walled carbon nanotube composite material provided by the embodiment of the invention, the micron-sized lithium titanate with a hierarchical structure not only has the high specific capacity and high rate capability of a nanoscale material, but also has the high tap density of the micron-sized material and the adaptability of industrial preparation; the multi-walled carbon nano tube with excellent conductivity is adopted to compositely modify the micron-sized lithium titanate, so that the defect that the electron conductivity of the lithium titanate is weaker is overcome, and the composite material not only has high specific capacity and high rate capability, but also has good conductive effect.
In some embodiments, the mass fraction of the multi-walled carbon nanotubes in the composite material is preferably 3 to 10%; and/or the particle size of the micron-sized lithium titanate is 2-3 mu m, the thickness of the nanoscale sheet is 5-8nm, and the width of the nanoscale sheet is 50-500nm.
In the embodiment of the invention, the dosage ratio of the micron-sized lithium titanate to the multi-walled carbon nanotube is optimized, so that the capacitance and the conductivity of the composite material are in a proper range, better comprehensive performance is achieved, and the composite material is more suitable for application in electrode materials; if the using amount of the multi-walled carbon nano-tube is too much, the mass of the electrode material is increased, and the mass specific capacity and the energy density of the battery are reduced; if the amount of the multi-walled carbon nanotube is too small, the conductivity of the electrode material is insufficient, and the rate capability of the electrode material is affected.
The embodiment of the invention also provides a preparation method of the micron-sized lithium titanate and multi-walled carbon nanotube composite material, which comprises the following steps:
(1) Adding the multi-walled carbon nano-tube into an acid solution for dispersion, heating and refluxing, and filtering to obtain a multi-walled carbon nano-tube A;
(2) Adding the multi-walled carbon nanotube A obtained in the step (1) into a surfactant solution to obtain a multi-walled carbon nanotube dispersion liquid B;
(3) Dispersing titanium dioxide in a concentrated alkali solution to perform hydrothermal reaction, dispersing the obtained product in a dilute alkali solution, adding hydrogen peroxide to perform heating reaction, performing acid exchange on the obtained product, and then dispersing in a lithium hydroxide solution to perform hydrothermal reaction to obtain micron-sized lithium titanate;
(4) And (3) dispersing the micron-sized lithium titanate obtained in the step (3) in water to obtain a micron-sized lithium titanate water dispersion, adding the multi-walled carbon nanotube dispersion B obtained in the step (2) into the micron-sized lithium titanate water dispersion, carrying out aging reaction, filtering, and annealing the obtained solid to obtain the composite material.
According to the preparation method of the composite material of the micron lithium titanate and the multi-wall carbon nano tube, after the surface modification treatment is carried out on the multi-wall carbon nano tube, the dispersion property and the charging property of the multi-wall carbon nano tube in an aqueous solution can be improved, so that the multi-wall carbon nano tube can be compounded with the micron lithium titanate with a hierarchical structure through electrostatic interaction, and the multi-wall carbon nano tube and the micron lithium titanate are uniformly compounded; the titanium dioxide is used as a titanium source to prepare the micron-sized lithium titanate with a hierarchical structure, and the material has dual properties of a nano-sized material and a micron-sized material and is suitable for application in batteries; the preparation method has the advantages of low energy consumption and simple process, and is suitable for popularization and application of industrial production.
In some embodiments, in the step (1), the ratio of the multi-walled carbon nanotubes to the acid solution is preferably 1 to 2g of the multi-walled carbon nanotubes per 500mL of the acid solution. Further preferably, in the step (1), the dispersion is ultrasonic dispersion, and the time of the ultrasonic dispersion is 2 to 8h. More preferably, the acid solution is a concentrated nitric acid solution or a mixed acid solution of concentrated nitric acid and sulfuric acid, and the volume ratio of nitric acid in the mixed acid solution is 80-95%.
In the embodiment of the invention, the dosage of the acid solution and the dispersion condition are optimized, so that the multi-walled carbon nanotube can be uniformly dispersed in the acid solution, the surface activity of the multi-walled carbon nanotube is effectively enhanced, and the subsequent modification treatment is facilitated.
In some embodiments, preferably, in the step (2), the mass ratio of the surfactant to the multi-walled carbon nanotube a is 1; the surfactant comprises at least one of octadecyl dimethyl benzyl quaternary ammonium chloride, hexadecyl trimethyl quaternary ammonium bromide, hexadecyl trimethyl quaternary ammonium chloride and dodecyl dimethyl benzyl ammonium chloride.
In the embodiment of the invention, the dosage and the type of the surfactant are optimized, the mass ratio of the surfactant to the multi-wall carbon nano tube A is optimized, and the surface of the multi-wall carbon nano tube can be uniformly coated by the surfactant; the tail part of the cationic surfactant has a hydrophobic group, the surface of the carbon nano tube also has hydrophobicity, the cationic surfactant and the hydrophobic group can be spontaneously attracted in water, so that the surface of the carbon nano tube is grafted with the surfactant, the surface of the carbon nano tube is modified, and the head part of the cationic surfactant has positive charges, so that the multi-walled carbon nano tube is in a positive charge state. If it is desired that the entire multi-walled carbon nanotube be negatively charged, it may be modified with an anionic surfactant.
In some embodiments, preferably, in the step (3), the temperature of the hydrothermal reaction is 120 to 180 ℃, and the time of the hydrothermal reaction is 12 to 24h; and/or the temperature of the heating reaction is 120 to 150 ℃, and the time of the heating reaction is 6 to 18h. Further preferably, in the step (3), the acid used for acid exchange is nitric acid with the acid content of 0.01 to 0.02M, and the time for acid exchange is not less than 72 hours. More preferably, the concentration of the lithium hydroxide solution is 0.1 to 0.3M. More preferably, the alkali solution is a sodium hydroxide solution, the concentration of the concentrated alkali solution is 10 mol/L, and the concentration of the dilute alkali solution is 2mol/L.
In the embodiment of the invention, a preparation method of the micron-sized lithium titanate is optimized, the micron-sized lithium titanate prepared by the method has a secondary structure with a nano size, and the shape of the micron-sized lithium titanate can be kept by slowly performing acid exchange with low-concentration nitric acid, so that the material has the high specific capacity and high rate capability of a nano-sized material, the high tap density of the micron-sized material and the adaptability of industrial preparation.
In some embodiments, preferably, in the step (4), the aging reaction time is 12 to 24h; and/or the temperature of the annealing treatment is 350 to 450 ℃, and the time of the annealing treatment is 4 to 8h.
The embodiment of the invention also provides an electrode material which comprises the composite material or the composite material prepared by the method.
The electrode material in the embodiment of the present invention has all the technical characteristics of the micron-sized lithium titanate and the multi-walled carbon nanotube composite material in the embodiment of the present invention, and therefore, has all the advantages and technical effects of the micron-sized lithium titanate and the multi-walled carbon nanotube composite material in the embodiment of the present invention, and are not described herein again.
The embodiment of the invention also provides a magnesium ion battery which comprises the electrode material.
Advantages and technical effects brought by the magnesium ion battery according to the embodiment of the present invention, the magnesium ion battery according to the embodiment of the present invention has all technical features of the electrode material according to the embodiment of the present invention, and therefore, all advantages and technical effects brought by the electrode material according to the embodiment of the present invention are not described herein again.
The present invention will be described in detail with reference to the following specific embodiments and the accompanying drawings.
Example 1
(1) Adding 2g of commercialized multi-walled carbon nano-tube into 500mL of mixed solution of concentrated nitric acid and sulfuric acid, wherein the volume ratio of the concentrated nitric acid is 80%, uniformly stirring the mixed solution, dispersing for 2h by using ultrasonic waves, heating and refluxing the mixed solution for 8h, and filtering to obtain a preliminarily treated multi-walled carbon nano-tube A with enhanced surface activity;
(2) Adding the multi-walled carbon nanotube A into a mixed solution of water and ethylene glycol containing 8g of octadecyl dimethyl benzyl quaternary ammonium chloride, and performing ultrasonic dispersion in a water bath overnight to obtain a multi-walled carbon nanotube dispersion liquid B;
(3) Dispersing titanium dioxide in an aqueous solution of sodium hydroxide, reacting for 24 hours at 120 ℃, dispersing a product into the aqueous solution of the sodium hydroxide with lower concentration, adding hydrogen peroxide, reacting for 6 hours at 150 ℃, slowly performing acid exchange by using 0.01mol/L nitric acid, continuously performing the acid exchange for 72 hours, replacing an acid solution every 24 hours in the middle, finally dispersing the product after the acid exchange into 0.25mol/L lithium hydroxide solution, and reacting for 24 hours at 120 ℃ to obtain micron-sized lithium titanate with a hierarchical structure;
(4) Dispersing micron-sized lithium titanate with a hierarchical structure into water, performing ultrasonic dispersion to obtain a micron-sized lithium titanate aqueous dispersion, dropwise adding a multi-walled carbon nanotube dispersion B into the lithium titanate aqueous dispersion in a stirring state according to a proportion, performing coagulation immediately after adding, aging for 12h, and annealing a solid obtained by filtering in the air at 350 ℃ for 8h to obtain a micron-sized lithium titanate/multi-walled carbon nanotube composite with a hierarchical structure, wherein the mass fraction of multi-walled carbon nanotubes in the composite is 5%.
The transmission electron micrograph of the composite material prepared in example 1 is shown in fig. 1, and the scanning electron micrograph is shown in fig. 2. As can be seen from fig. 1 and 2, the lithium titanate is in the form of micron-sized spherical particles, the spherical particles are formed by cross-stacking nanoscale flakes, and the multi-walled carbon nanotubes are uniformly distributed on the surface of the spherical particles.
An impedance spectrum before and after the micron-sized lithium titanate composite multi-walled carbon nanotube in the embodiment is shown in fig. 3, wherein the impedance spectrum is tested by an electrochemical workstation, the frequency range is set to be 0.01 to 1000000 Hz, the voltage is set to be open-circuit voltage, and the amplitude is 50mV. As can be seen from FIG. 3, the electrical conductivity of lithium titanate is greatly improved after the lithium titanate is compounded with the multi-wall carbon nano tube.
Example 2
(1) Adding 4g of commercialized multi-walled carbon nano-tube into 1000mL of mixed solution of concentrated nitric acid and sulfuric acid, wherein the volume ratio of the concentrated nitric acid is 95%, uniformly stirring the mixed solution, dispersing for 8h by using ultrasonic waves, heating and refluxing the mixed solution for 12h, and filtering to obtain a preliminarily treated multi-walled carbon nano-tube A with enhanced surface activity;
(2) Adding the multi-walled carbon nanotube A into a mixed solution of water and ethylene glycol containing 10g of octadecyl dimethyl benzyl quaternary ammonium chloride, and performing ultrasonic dispersion in a water bath overnight to obtain a multi-walled carbon nanotube dispersion liquid B;
(3) Dispersing titanium dioxide in an aqueous solution of sodium hydroxide, reacting for 12 hours at 180 ℃, dispersing a product into an aqueous solution of sodium hydroxide with a lower concentration, adding hydrogen peroxide, reacting for 18 hours at 120 ℃, slowly performing acid exchange by using 0.01mol/L nitric acid, continuously performing acid exchange for 96 hours, replacing an acid solution every 24 hours, finally dispersing the product after the acid exchange into a 0.25mol/L lithium hydroxide solution, and reacting for 12 hours at 160 ℃ to obtain micron-sized lithium titanate with a hierarchical structure;
(4) Dispersing micron-sized lithium titanate with a hierarchical structure into water, performing ultrasonic dispersion to obtain a micron-sized lithium titanate aqueous dispersion, dropwise adding a multi-walled carbon nanotube dispersion B into the lithium titanate aqueous dispersion in a stirring state according to a proportion, performing coagulation immediately after adding, aging for 24 hours, and annealing a solid obtained by filtering in the air at 450 ℃ for 4 hours to obtain a micron-sized lithium titanate/multi-walled carbon nanotube composite with a hierarchical structure, wherein the mass fraction of multi-walled carbon nanotubes in the composite is 5%.
Comparative example 1
Comparative example 1 was prepared in the same manner as in example 1 except that: the micron-sized lithium titanate without a hierarchical structure is prepared in the step (3).
The preparation method of the micron-sized lithium titanate comprises the following steps: adding tetrabutyl titanate into ethylene glycol dropwise to obtain a solution A, dissolving 9mmol of LiOH in 30mL of deionized water to obtain a solution B, and mixing A and B so that the molar ratio of Li to Ti is 0.9; and transferring the mixed solution to a hydrothermal kettle, reacting at 170 ℃ for 36 hours, washing and drying the obtained product, and calcining at 600 ℃ for 2 hours in the air.
Comparative example 2
Comparative example 2 was prepared in the same manner as in example 1, except that: the nano lithium titanate is prepared in the step (3).
The preparation method of the nanoscale lithium titanate comprises the following steps: 1.7mL of tetrabutyltitanate and 0.189g of lithium hydroxide monohydrate were added to 25mL of ethanol and vigorously stirred in a dry environment for 12 hours; then 25mL of deionized water is added, and the mixture is stirred vigorously for 1min; and transferring the mixture to a hydrothermal kettle, reacting at 180 ℃ for 36 hours, collecting the solid deposited at the bottom after the reaction is finished, washing the solid for three times by using deionized water, drying the obtained solid, and calcining the solid in the air at 600 ℃ for 2 hours.
Comparative example 3
This comparative example used the micron-sized lithium titanate having a hierarchical structure prepared by the method of example 1 without coating the multi-walled carbon nanotube.
The composite materials prepared in examples 1 to 2 and comparative examples 1 to 2 and the performance of the micron-sized lithium titanate having a hierarchical structure prepared in comparative example 3 were tested.
The composite material is respectively mixed with conductive carbon black (Super P) as a conductive agent and polyvinylidene fluoride as a binderThe alkene (PVDF) is mixed according to the mass ratio of 7 2 (ii) a Magnesium metal is used as a negative electrode, and an all-phenyl complex/tetrahydrofuran (APC/THF) is used as an electrolyte to assemble a magnesium ion battery, and the performance of the magnesium ion battery is tested, and the test results are shown in Table 1 and FIG. 4.
The test method comprises the following steps: the assembled blue electricity test system for the battery is tested in a constant current charging and discharging mode, and the specific capacity of the magnesium ion battery is respectively measured under the current densities of 20 mA/g, 50 mA/g and 100 mA/g.
TABLE 1
In the present disclosure, the terms "one embodiment," "some embodiments," "an example," "a specific example," or "some examples" and the like mean that a specific feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present disclosure. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Moreover, various embodiments or examples and features of various embodiments or examples described in this specification can be combined and combined by one skilled in the art without being mutually inconsistent.
Although the above embodiments have been shown and described, it should be understood that they are exemplary and not intended to limit the invention, and that various changes, modifications, substitutions and alterations can be made herein by those skilled in the art without departing from the scope of the invention.
Claims (10)
1. The composite material is characterized in that the micron-sized lithium titanate is micron-sized spherical particles and is formed by cross-stacking nanoscale sheets, and the multi-wall carbon nanotubes are distributed on the surface of the micron-sized lithium titanate.
2. The composite of lithium titanate and multi-walled carbon nanotubes of claim 1, wherein the composite comprises multi-walled carbon nanotubes in a mass fraction of 3 to 10%; and/or the particle size of the micron-sized lithium titanate is 2-3 mu m, the thickness of the nanoscale sheet is 5-8nm, and the width of the nanoscale sheet is 50-500nm.
3. A preparation method of a micron-sized lithium titanate and multi-walled carbon nanotube composite material is characterized by comprising the following steps:
(1) Adding the multi-walled carbon nanotube into an acid solution for dispersion, heating and refluxing, and filtering to obtain a multi-walled carbon nanotube A;
(2) Adding the multi-walled carbon nano-tube A obtained in the step (1) into a surfactant solution to obtain a multi-walled carbon nano-tube dispersion liquid B;
(3) Dispersing titanium dioxide in a concentrated alkali solution to perform hydrothermal reaction, dispersing the obtained product in a dilute alkali solution, adding hydrogen peroxide to perform heating reaction, performing acid exchange on the obtained product, and then dispersing in a lithium hydroxide solution to perform hydrothermal reaction to obtain micron-sized lithium titanate;
(4) And (3) dispersing the micron-sized lithium titanate obtained in the step (3) in water to obtain a micron-sized lithium titanate water dispersion, adding the multi-walled carbon nanotube dispersion B obtained in the step (2) into the micron-sized lithium titanate water dispersion, carrying out aging reaction, filtering, and annealing the obtained solid to obtain the composite material.
4. The method for preparing the micron-sized lithium titanate and multi-walled carbon nanotube composite material according to claim 3, wherein in the step (1), the ratio of the multi-walled carbon nanotube to the acid solution is 1-2g of the multi-walled carbon nanotube per 500mL of the acid solution.
5. The preparation method of the micron-sized lithium titanate and multi-walled carbon nanotube composite material according to claim 3, wherein in the step (2), the mass ratio of the surfactant to the multi-walled carbon nanotube A is 1; the surfactant comprises at least one of octadecyl dimethyl benzyl quaternary ammonium chloride, hexadecyl trimethyl quaternary ammonium bromide, hexadecyl trimethyl quaternary ammonium chloride and dodecyl dimethyl benzyl ammonium chloride.
6. The method for preparing the micron-sized lithium titanate and multi-walled carbon nanotube composite material according to claim 3, wherein in the step (3), the temperature of the hydrothermal reaction ranges from 120 ℃ to 180 ℃, and the time of the hydrothermal reaction ranges from 12 to 24h; and/or the temperature of the heating reaction is 120 to 150 ℃, and the time of the heating reaction is 6 to 18h.
7. The method for preparing the micron-sized lithium titanate and multi-walled carbon nanotube composite material according to claim 3 or 6, wherein in the step (3), the acid exchange adopts nitric acid with the acid content of 0.01 to 0.02M, and the acid exchange time is not less than 72 hours.
8. The method for preparing a micron-sized lithium titanate and multi-walled carbon nanotube composite material according to claim 3, wherein in the step (4), the aging reaction time is 12 to 24h; and/or the temperature of the annealing treatment is 350 to 450 ℃, and the time of the annealing treatment is 4 to 8h.
9. An electrode material comprising the composite material according to claim 1 or 2 or the composite material produced by the method according to any one of claims 3 to 8.
10. A magnesium-ion battery comprising the electrode material according to claim 9.
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