CN107134575B - Preparation method of sodium ion battery negative electrode material - Google Patents
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- CN107134575B CN107134575B CN201710202293.5A CN201710202293A CN107134575B CN 107134575 B CN107134575 B CN 107134575B CN 201710202293 A CN201710202293 A CN 201710202293A CN 107134575 B CN107134575 B CN 107134575B
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- H—ELECTRICITY
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- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- H—ELECTRICITY
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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Abstract
The invention discloses a preparation method of a sodium ion battery cathode material. The titanium source and other two kinds of hetero-atom compounds are sequentially subjected to sol-gel, heat treatment, concentrated alkali soaking, high-temperature calcination and the like to prepare the hetero-atom co-doped titanium dioxide nanotube sodium ion battery cathode material. The hetero-atom co-doped titanium dioxide nanotube prepared by the method through simple and common equipment has uniform appearance, excellent conductivity and improved ion diffusion rate, so that the hetero-atom co-doped titanium dioxide nanotube has excellent electrochemical properties such as large sodium storage capacity, good cycle performance, high coulombic efficiency and the like. The preparation method has the advantages of simple preparation process, easily available raw materials, low cost, environmental friendliness, high repeatability, high yield, contribution to industrial production and wide commercial application prospect.
Description
Technical Field
The invention relates to a sodium ion battery, in particular to a preparation method of a sodium ion battery cathode material.
Background
Energy is the material basis on which humans live and develop. With the increase of population and economy, the demand of human society for energy is increasing. Lithium ion batteries have been widely used in the field of energy storage due to their advantages of high energy density, long cycle life, no memory effect, etc. However, in consideration of the problems of cost, safety performance, lithium resource scarcity and the like of the lithium ion battery, a replaceable energy storage system with richer resources, cheaper resources and higher safety is urgently needed to be found.
Sodium ion batteries are similar battery systems to lithium ion batteries. On one hand, sodium and lithium are metals in the same main group, the performances are relatively close, and sodium resources on the earth are richer than lithium resources. On the other hand, the potential of the sodium-ion half cell is about 0.3V higher than that of the lithium-ion half cell, and the sodium-ion half cell is suitable for a liquid electrolyte system with excellent electrochemical performance but low decomposition voltage and has higher safety. Therefore, sodium ion batteries have been increasingly studied worldwide in recent years. However, since the radius of sodium ions is larger than that of lithium ions and the reaction kinetics thereof are slower, the cycle performance of the battery is poor and the reversible specific capacity is low. In order to solve the problems, the search for a suitable sodium ion battery electrode material is very important. Currently, the positive electrode material of sodium ion battery has been widely studied and made some progress, but the bottleneck still exists in the negative electrode material with long cycle life and good rate performance. The carbon material used by the commercial lithium ion battery can not avoid potential safety hazard caused by sodium dendrite growth due to too low voltage platform (< 0.1V); although the alloy material has higher theoretical specific capacity, the battery material has unstable structure and short cycle life due to huge volume expansion. Therefore, the development of a novel and cheap negative electrode material with high specific capacity and good cycling stability is the key for improving the performance of the sodium-ion battery.
The titanium dioxide is a sodium ion negative electrode material with a very promising prospect due to the advantages of low sodium storage potential (approximately equal to 0.7V), high theoretical specific capacity (335 mAh g-1), low price, easy obtainment, good safety performance and the like. However, the charge/discharge performance of titanium dioxide is poor due to the defects of low conductivity, low ion mobility and the like. Hetero-atom doping is a common and highly effective method for improving the electrochemical performance of titanium dioxide. Jiangfeng Ni (adv. mater. 2016, DOI: 10.1002/adma.201504412) and the like synthesize a sulfur-doped titanium dioxide nanotube array for the first time, and the sulfur-doped titanium dioxide nanotube array is used as a negative electrode material to be applied to a sodium ion battery system and obtains excellent electrochemical performance. However, in the preparation process, titanium dioxide doping needs to be performed at a high temperature by using elemental sulfur as a sulfur source, which easily causes huge potential safety hazards. On the other hand, the experimental process is complicated, and the material prepared by the electrochemical deposition method used has poor uniformity. In addition, chinese patent application No. 201410328415.1 discloses "a titanium oxide negative electrode material useful as a sodium ion battery and a method for preparing the same", which prepares a titanium oxide doped with a single property element as a negative electrode material of a sodium ion battery. Due to the limitation of thermodynamic properties, part of the doping elements may be doped into the poor gaps of the crystal lattice, thereby causing the conductivity of the titanium oxide not to be increased or even deteriorated, and also its thermodynamic stability to be deteriorated. On the other hand, the titanium oxide prepared by the patent has defects in morphology, and further influences the electrochemical performance of the sodium-ion battery.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of a sodium-ion battery cathode material which is low in energy consumption, pollution-free and easy to industrially produce.
In order to solve the technical problems, the technical scheme provided by the invention is as follows: a preparation method of a sodium-ion battery negative electrode material comprises the following steps: 1) the preparation of the different atom co-doped titanium dioxide precursor,
dispersing a titanium source compound into short-chain unit alcohol at a mixing ratio of 1:2-1:8, and magnetically stirring for 10-30 minutes to obtain a clear and uniform mixed solution
(ii) a The titanium source compound is one or more of tetrabutyl titanate, tetraethyl titanate, titanium tetrachloride, tetraisopropyl titanate and propyl titanate; the short-chain unit alcohol is one or more of methanol, ethanol, propanol, n-butanol and isobutanol; the titanium source compounds used in the invention have the following characteristics: easy hydrolysis, easy control of the dissolution speed, and the particle size and morphology suitable for the invention can be achieved after the short chain unit alcohol is added.
the hetero-atom co-doped titanium dioxide is of a nano tubular structure, the outer diameter is 4-15 nm, the inner diameter is 2-8 nm, and the length is 20-100 nm.
2) The preparation of the hetero-atom co-doped titanium dioxide nanotube,
dispersing the different-atom co-doped titanium dioxide precursor obtained in the step 1) in a concentrated alkali solution according to a solid-to-liquid ratio of 5-20 g/L, so as to uniformly disperse ions doped in the titanium dioxide precursor in crystal lattices, stirring for 1-4 hours, transferring the titanium dioxide precursor into a sealed high-pressure kettle, storing at 120-180 ℃ for 10-24 hours, and naturally cooling;
3) and (3) preparing the hetero-atom co-doped titanium dioxide nanotube obtained in the step (2) into a negative electrode of a secondary sodium-ion battery or a negative electrode of a capacitor.
In the preparation method of the sodium-ion battery cathode material, preferably, the metal compound is one or more of iron, copper, nickel, cobalt, tin, chromium, lead, zinc or a rare earth metal compound; the non-metallic compound is one or more of sulfur, boron, nitrogen, carbon or halogen element compounds.
In the preparation method of the negative electrode material of the sodium-ion battery, preferably, the concentrated alkali is one or two of sodium hydroxide and potassium hydroxide.
In the preparation method of the sodium-ion battery negative electrode material, preferably, the dilute acid solution is one or more of dilute hydrochloric acid, dilute sulfuric acid or dilute nitric acid; the concentration of the dilute acid solution is 0.1-0.5 mol/L.
In the preparation method of the sodium ion battery cathode material, preferably, the atomic number percentage of the metal element in the hetero-atom co-doped titanium dioxide nanotube is 0.01-5%, the doping amount can promote the transformation between crystal phases and influence the crystal morphology, but when the doping amount is too high, the crystal lattice can be seriously distorted, so that part of the tubes are easy to crack, and the size of the obtained nanotubes can be relatively reduced; the atomic percentage of the non-metal elements in the different-atom co-doped titanium dioxide nanotube is 0.1-5%. The structure and the conductivity of the titanium dioxide can be improved by doping the titanium dioxide with the metal element.
In the preparation method of the negative electrode material of the sodium-ion battery, preferably, the hetero-atom co-doped titanium dioxide nanotube is one or two of an anatase phase and a rutile phase.
Compared with the prior art, the invention has the advantages that: (1) according to the invention, the energy band gap of the titanium dioxide is reduced under the action of the different atom co-doping, so that the inherent electronic conductivity and ionic conductivity of the titanium dioxide are improved. In addition, the co-doping system can better provide an acceptor or a donor, respectively providing electrons or binding electrons, so that the thermodynamics of the material are more stable. (2) The hetero-atom co-doped titanium dioxide prepared by the method is of a nano tubular structure with high mechanical strength. The structure has uniform size and large specific surface area, can greatly shorten the migration distance of ions and electrons, is favorable for full contact of an electrode material and electrolyte, and further improves the electrochemical performance of the sodium-ion battery. (3) The method has the advantages of convenient operation, low energy consumption, no pollution, strong repeatability and no need of expensive equipment, and is suitable for industrial batch production. The prepared hetero-atom co-doped titanium dioxide nanotube is an ideal cathode material for the sodium-ion battery. (4) The raw materials required by the invention are cheap and easy to obtain, and the method is easy for large-scale production.
In conclusion, the method which is low in energy consumption, pollution-free and easy to industrially synthesize is designed to prepare the hetero-atom co-doped titanium dioxide sodium ion cathode material with the high conductivity and the nano-tube structure, so that the excellent electrochemical properties such as high sodium storage capacity, long cycle life and good rate performance are realized.
Drawings
FIG. 1 is a flow chart of the preparation of the hetero-atom co-doped titanium dioxide nanotube of the present invention.
FIG. 2 is an XRD analysis pattern obtained in example 1 of the present invention.
FIG. 3 is a TEM image obtained in example 1 of the present invention.
FIG. 4 is a graph of cycle performance for inventive example 2 and comparative example.
FIG. 5 is a graph showing the magnification in example 2.
Detailed Description
In order to facilitate an understanding of the present invention, the present invention will be described more fully and in detail with reference to the preferred embodiments, but the scope of the present invention is not limited to the specific embodiments described below.
It should be particularly noted that when an element is referred to as being "fixed to, connected to or communicated with" another element, it can be directly fixed to, connected to or communicated with the other element or indirectly fixed to, connected to or communicated with the other element through other intermediate connecting components.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Example 1
10mL of tetraisopropyl titanate was added to 20mL of propanol and magnetically stirred for 30 minutes to give clear and homogeneous mixed solution 1. 0.6g of urea and 0.25g of Cu (NO) were added3)2·3H2O was dissolved well in 50mL propanol and stirred for 60 minutes to give well mixed clear solution 2. And then, slowly adding the solution 1 into the solution 2 drop by drop, sequentially carrying out magnetic stirring for 3 hours, standing and aging for 10 hours, storing at 100 ℃ until the supernatant is completely evaporated to obtain a gel-like substance, fully grinding, calcining at 600 ℃ for 2 hours, and naturally cooling to obtain the copper and nitrogen co-doped titanium dioxide precursor.
Dispersing 2g of the precursor in 8mol/L KOH solution, stirring for 4 hours, transferring the mixture into an autoclave, preserving the mixture for 10 hours at 180 ℃, and naturally cooling the mixture. Then respectively using 0.2mol/L HNO3The solution was washed with deionized water until the pH was neutral. And then drying the materials at 50 ℃, putting the materials into a muffle furnace for high-temperature calcination treatment at 600 ℃ for 4 hours, and cooling the materials to room temperature to obtain the high-performance copper-nitrogen co-doped titanium dioxide nanotube.
Preparing an electrode of the copper-nitrogen co-doped titanium dioxide nanotube negative electrode material and testing electrochemical properties:
the copper-nitrogen co-doped titanium dioxide nanotube negative electrode material prepared in example 1, conductive carbon and a binder (PVDF) were thoroughly mixed in a mass ratio of 7:2:1, and were manually ground using N-methyl-2-pyrrolidone (NMP) as a dispersant to obtain a uniform slurry. Coating the obtained slurry on a copper foil, putting the copper foil into a vacuum oven at 60 ℃ for drying for 12 h, and then beating into a disk-shaped pole piece with the diameter of 10 mm. Then the electrode sheet is taken as a working electrode, a metal sodium sheet is taken as a reference electrode, whatman glass fiber is taken as a diaphragm, and 1mol/L NaClO4The electrolyte solution of/EC + DEC/5% FEC, in argon filled glove box assembled into CR2032 button cell. At room temperature (25 ℃ C.)And limiting the voltage to 0.1-2.5V to perform constant-current charge and discharge tests. XRD (X-ray diffraction) and TEM (transmission electron microscope) images of the copper-nitrogen co-doped titanium dioxide cathode material prepared in the embodiment 1 of the invention are respectively shown in fig. 2 and fig. 3.
Test results show that the structure of the copper-nitrogen co-doped titanium dioxide prepared by the method is a nano-tube structure, wherein the copper content is 0.2 at%, and the nitrogen content is 0.3 at%. XRD shows that the crystal form of the material is anatase phase titanium dioxide. At a current level of 0.1A g-1The first discharge specific capacity of the battery is 579.4 mA h g-1And the specific capacity after 120 cycles is 155.8 mA h g-1。
Example 2
5mL of tetrabutyl titanate is dissolved in 20mL of absolute ethanol, and the solution is magnetically stirred for 20 minutes to obtain a uniformly mixed clear solution 1. Adding 0.274g of thiourea into 20mL of absolute ethyl alcohol, fully dissolving, adding 0.48g of FeCl3·6H2And O, continuously stirring for 30 minutes to obtain a mixed solution 2. And then slowly dropwise adding the solution 1 into the solution 2, sequentially carrying out magnetic stirring for 2 hours, standing and aging for 12 hours, preserving at 80 ℃, grinding and transferring to a muffle furnace for calcining for 3 hours at 500 ℃ after the solvent is completely evaporated, and cooling to obtain the precursor of the iron-sulfur co-doped titanium dioxide.
1.2g of the precursor was dispersed in 100mL of a 10mol/L NaOH solution, stirred for 2 hours, and then transferred to a high-pressure reactor and stored at 150 ℃ for 12 hours. After cooling at room temperature, the solution is washed by 0.1mol/L HCl solution and deionized water respectively until the pH value of the solution is neutral. And transferring the dried mixture to a muffle furnace to calcine the mixture for 2 hours at 500 ℃, and naturally cooling the mixture to obtain the iron-sulfur co-doped titanium dioxide nanotube.
The electrochemical performance test was the same as in example 1. The cycle performance curve and the rate curve of the iron-sulfur co-doped titanium dioxide nanotube prepared in example 2 of the present invention are shown in fig. 4 and 5, respectively.
Test results show that the iron content and the sulfur content of the iron-sulfur co-doped titanium dioxide prepared by the method are 2 at% and 0.25 at%. XRD shows that the crystal form of the material is anatase phase titanium dioxide. At a current level of 0.1A g-1The first discharge specific capacity of the battery is 531.1 mA h g-1The specific capacity after 100 cycles is 177.1 mA h g-1. In addition, when the current magnitude is respectively 0.05, 0.1, 0.2, 0.5, 1, 2A g-1When the discharge capacity is higher than the standard value, the discharge specific capacities are respectively 238, 192, 156,110, 82 and 59 mA h g-1After 60 cycles, the current will be 0.1A g-1The discharge specific capacity of the material is recovered to 190 mA hg-1。
Example 3
10mL of tetraethyl titanate was dispersed in 30mL of butanol and magnetically stirred for 10 minutes to give clear mixed solution 1. 0.6g of boric acid and 4g of Cr (SO) were further added4)3Fully dissolving in butanol, and magnetically stirring for 20-minutes to obtain a uniformly mixed clear solution 2. And then, slowly adding the solution 1 into the solution 2 drop by drop, sequentially carrying out magnetic stirring for 4 hours, standing and aging for 24 hours, then, storing for 15 hours at 60 till the supernatant is completely evaporated to obtain a gelatinous substance, fully grinding, calcining for 5 hours at 300 ℃, and naturally cooling to obtain the chromium-boron co-doped titanium dioxide precursor.
1g of the precursor is dispersed in 50mL of 15mol/L KOH solution, stirred for 4 hours, transferred to an autoclave, stored at 120 ℃ for 24 hours, and naturally cooled. Followed by the addition of 0.5mol/L of H respectively2SO4The solution was washed with deionized water until the pH was neutral. And then drying the materials at 100 ℃, putting the materials into a muffle furnace for high-temperature calcination treatment at 400 ℃ for 5 hours, and cooling to room temperature to obtain the high-performance chromium-boron co-doped titanium dioxide nanotube.
Preparing an electrode of the chromium-boron co-doped titanium dioxide nanotube negative electrode material and testing electrochemical properties:
the chromium-boron co-doped titanium dioxide nanotube negative electrode material prepared in the example 3, conductive carbon and a binder (CMC) are fully mixed according to the mass ratio of 8:1:1, deionized water is used as a dispersing agent, and the mixture is manually ground to obtain uniform slurry. Coating the obtained slurry on a copper foil, putting the copper foil into a vacuum oven at 60 ℃ for drying for 12 h, and then forming a disk-shaped pole piece with the diameter of 10 mm. Then the pole piece is taken as a working electrode, a metal sodium piece is taken as a reference electrode, Cegard 2300 is taken as a diaphragm, and 1mol/L of NaClO4using/EC + DMC/5% FEC as electrolyte, chargingThe glove box filled with argon was assembled into a CR2025 button cell. The constant current charge and discharge test is carried out at room temperature (25 ℃) and the limiting voltage is 0.1-2.5V and 1A/g. The XRD pattern of example 3 of the present invention is shown in fig. 2.
Test results show that the chromium-codoped boron titanium dioxide nanotube prepared by the method is anatase-phase titanium dioxide. At a current level of 1A g-1The first discharge specific capacity of the battery is 373.1 mA h g-1And the specific capacity is 73.2 mA h g after 1000 cycles-1。
Comparative example:
dissolving 5mL of tetrabutyl titanate in 20mL of absolute ethyl alcohol, magnetically stirring for 20 minutes to obtain a uniformly mixed clear solution, sequentially magnetically stirring for 2 hours, standing and aging for 12 hours, storing at 80 ℃ for 12 hours, completely evaporating the solvent, grinding, transferring to a muffle furnace, calcining at 500 ℃ for 3 hours, and cooling to obtain a crude product of titanium dioxide.
1.2g of the crude product was dispersed in 100mL of a 10mol/L NaOH solution, stirred for 2 hours, and then transferred to an autoclave and stored at 150 ℃ for 12 hours. After cooling at room temperature, the solution is washed by 0.1mol/L HCl solution and deionized water respectively until the pH value of the solution is neutral. And transferring the dried titanium dioxide nanotube to a muffle furnace to calcine the titanium dioxide nanotube for 2 hours at 500 ℃, and naturally cooling the titanium dioxide nanotube to obtain the titanium dioxide nanotube.
The electrochemical performance test was the same as in example 1. XRD and cycle performance curves of the titanium dioxide nanotubes prepared by the comparative example of the present invention are shown in fig. 2 and 4, respectively.
The test results showed that the titanium dioxide nanotubes prepared by the comparative example were a mixture of anatase phase and rutile phase titanium dioxide. At a current level of 0.1A g-1The first discharge specific capacity of the battery is 219.6 mA h g-1The specific capacity after 100 cycles is 41.5 mA h g-1. It can be seen that the electrical performance parameters of the titanium dioxide nanotubes prepared by the comparative example are significantly lower than those of examples 1,2 and 3.
Claims (5)
1. A preparation method of a sodium ion battery cathode material is characterized by comprising the following steps of 1) preparation of an isoatom co-doped titanium dioxide precursor, ① dispersion of a titanium source compound in short-chain unit alcohol with a mixing ratio of 1:2-1:8, magnetic stirring for 10-30 minutes to obtain a clear and uniform mixed solution I, wherein the titanium source compound is one or more of tetrabutyl titanate, tetraethyl titanate, titanium tetrachloride, tetraisopropyl titanate and propyl titanate, and the short-chain unit alcohol is one or more of methanol, ethanol, propanol, n-butanol and isobutanol;
② dissolving one or more of soluble iron, copper, nickel, cobalt, tin, chromium, lead, zinc or rare earth metal compounds and one or more of sulfur, boron, nitrogen, carbon or halogen element compounds in short chain alcohol completely, and magnetically stirring for 20-60 min to obtain uniformly mixed clear solution II;
③ slowly adding the solution I dropwise into the solution II, magnetically stirring for 2-4 hr, standing and aging for 10-24 hr, and storing at 60-100 deg.C until the supernatant is completely evaporated to obtain gel;
④, fully grinding, calcining at the temperature of 300-800 ℃ for 1-5 hours, and naturally cooling to obtain the hetero-atom co-doped titanium dioxide precursor;
2) preparing a different atom co-doped titanium dioxide nanotube, namely ① dispersing the different atom co-doped titanium dioxide precursor obtained in the step 1) in a concentrated alkali solution according to a solid-to-liquid ratio of 5-20 g/L, stirring for 1-4 hours, transferring to a sealed autoclave, storing at 120-180 ℃ for 10-24 hours, and naturally cooling;
②, filtering the solution obtained in the step ①, washing the obtained solid to neutrality by using a dilute acid solution and deionized water, then drying at 50-100 ℃, calcining at 400-800 ℃ for 2-8 hours, and cooling to room temperature to obtain the hetero atom co-doped titanium dioxide nanotube;
and (3) preparing the hetero-atom co-doped titanium dioxide nanotube obtained in the step (2) into a negative electrode of a secondary sodium-ion battery or a negative electrode of a capacitor.
2. The method for preparing the negative electrode material of the sodium-ion battery according to claim 1, wherein: the concentrated alkali is one or two of sodium hydroxide and potassium hydroxide.
3. The method for preparing the negative electrode material of the sodium-ion battery according to claim 1, wherein: the dilute acid solution is one or more of dilute hydrochloric acid, dilute sulfuric acid or dilute nitric acid; the concentration of the dilute acid solution is 0.1-0.5 mol/L.
4. The method for preparing the negative electrode material of the sodium-ion battery according to claim 1, wherein: the atomic number percentage content ratio of the metal elements in the different-atom co-doped titanium dioxide nanotube is 0.01-5%; the atomic percentage of the non-metal elements in the different-atom co-doped titanium dioxide nanotube is 0.1-5%.
5. The method for preparing the negative electrode material of the sodium-ion battery according to claim 1, wherein: the hetero-atom co-doped titanium dioxide nanotube is one or two of an anatase phase and a rutile phase.
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| CN112886013B (en) * | 2021-01-28 | 2022-11-08 | 陕西科技大学 | Preparation method of titanium dioxide/carbon nanofiber anode material with multilevel structure |
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