CN115295760A - Nano carbon layer coated titanium dioxide electrode containing oxygen defects, preparation method thereof and magnesium battery - Google Patents

Nano carbon layer coated titanium dioxide electrode containing oxygen defects, preparation method thereof and magnesium battery Download PDF

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CN115295760A
CN115295760A CN202210859997.0A CN202210859997A CN115295760A CN 115295760 A CN115295760 A CN 115295760A CN 202210859997 A CN202210859997 A CN 202210859997A CN 115295760 A CN115295760 A CN 115295760A
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赵金保
武东政
曾静
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Xiamen University
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Abstract

The invention discloses a nano carbon layer coated titanium dioxide electrode containing oxygen defects, a preparation method thereof and a magnesium battery. The electrode is composed of a current collector and an active material layer; tiO obtained by chemical treatment of dopamine solutions 2 Electrodes comprising not only a controlled growth nano-scale carbon coating but also on TiO 2 Oxygen defects are introduced into the crystal structure, so that the active material layer grows on the surface of the current collector, a three-dimensional structure is formed by arranging and stacking a plurality of nanorod arrays, the nanorods are titanium dioxide containing the oxygen defects, and the surface of the titanium dioxide is coated with a nano carbon layer. The battery comprises a positive electrode, a diaphragm, electrolyte and a negative electrode, wherein the positive electrode adopts the electrode, the diaphragm is made of glass fiber, the electrolyte is 0.4M MgPhCl/THF, and the negative electrode is a magnesium sheet. Mg for magnesium metal battery system 2+ Slow diffusion in titanium dioxide, and poor cycle performance and rate capability.

Description

Nano carbon layer coated titanium dioxide electrode containing oxygen defects, preparation method thereof and magnesium battery
Technical Field
The invention belongs to the technical field of magnesium batteries, and particularly relates to a nano carbon layer coated titanium dioxide electrode with oxygen defects, a preparation method of the nano carbon layer coated titanium dioxide electrode and a magnesium battery.
Background
In recent years, batteries have been widely used as excellent energy storage systems in daily production and life, but in recent years, lithium (ion) batteries which are mainstream have problems of high safety and high price, and thus, scientists have made an attempt to find a new type of secondary battery which can replace lithium (ion) batteries. The magnesium battery has ultrahigh volume specific capacity (3833 mA h/cm) 3 ) The advantages of low price and uneasy generation of dendrites are considered to be one of the most potential energy storage systems for replacing lithium (ion) batteries.
Despite such many advantages of magnesium batteries, since the diffusion kinetics of magnesium ions in the cathode material are very slow due to the strong charge density of magnesium ions and the electron conductivity of the cathode material suitable for magnesium batteries is generally low, these problems seriously affect the reaction kinetics of the cathode side in magnesium batteries, and it is very important to develop a novel cathode material having high capacity, long cycle life and suitability for magnesium batteries. Titanium dioxide is beneficial to Mg due to the pore structure thereof 2+ Can realize reversible storage of Mg 2+ However, its specific mass capacity and cyclabilityThe energy and rate performance is poor due to poor electron conductivity and ion conductivity.
In addition, most of the conventional positive electrodes are electrodes formed by blending a binder, a conductive agent and an active material, the binder and the conductive agent cannot be completely and uniformly dispersed around the active material when being blended with the active material, so that the electrochemical performance of the electrodes is poor, the active material may fall off due to volume expansion/contraction in the repeated charging and discharging process, and the energy density of the battery is reduced due to the introduction of the binder and the conductive agent.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides the titanium dioxide electrode coated with the nano carbon layer and having the oxygen-containing defect, the preparation method thereof and the magnesium battery, solves the problems of dispersion and electrochemical performance of electrode active substances in the background technology, and further solves the performance problem of the magnesium battery.
One of the technical schemes adopted by the invention for solving the technical problems is as follows: the nano carbon layer coated titanium dioxide electrode containing the oxygen defects is composed of a current collector and an active material layer; the current collector is a titanium foil; the active material layer grows on the surface of the current collector and comprises a three-dimensional structure formed by stacking a plurality of nanorod arrays, and ion transmission pore canals are formed among the three-dimensional structures; the nano rod is made of titanium dioxide with oxygen defects, and the surface of the nano rod is coated with a nano carbon layer with controllable growth.
In a preferred embodiment of the present invention, the carbon nano-layer has a thickness of 5-50nm and is uniformly and continuously disposed on the surface of the titanium dioxide.
In a preferred embodiment of the present invention, the width of the nanorods is 50-100nm wide, and the length is 0.5-10 μm.
In a preferred embodiment of the present invention, the thickness of the active material layer is 10 to 100 μm.
In a preferred embodiment of the present invention, the nano carbon layer is formed by infiltrating nanorods with a mixed solution of dopamine hydrochloride and tris (hydroxymethyl) aminomethane, and then calcining and carbonizing the nanorods.
The second technical scheme adopted by the invention for solving the technical problems is as follows: the preparation method of the oxygen-defect-containing nano carbon layer-coated titanium dioxide electrode comprises the following steps:
(1) Dissolving sodium hydroxide in a mixed solution of deionized water and ethanol;
(2) Putting the titanium foil into the mixed solution, and reacting for 2-20h at 120-220 ℃ to obtain a reaction intermediate;
(3) Soaking the reaction intermediate in dilute hydrochloric acid for 1-20h, then washing with water and naturally airing;
(4) After the reaction intermediate is completely dried, calcining the reaction intermediate in a muffle furnace at the high temperature of 200-800 ℃ for 1-8h to obtain a titanium dioxide electrode with a three-dimensional structure formed by stacking a nanorod array;
(5) Soaking the obtained titanium dioxide electrode in a mixed solution of dopamine hydrochloride and tris (hydroxymethyl) aminomethane for 1-20h until the mixed solution fills a three-dimensional structure gap to obtain a polydopamine-coated titanium dioxide electrode;
(6) And calcining the soaked electrode at high temperature of 200-800 ℃ for 1-5h in an inert atmosphere to obtain the oxygen-defect-containing carbon-coated titanium dioxide electrode.
In a preferred embodiment of the invention, in the step (1), the volume ratio of the deionized water to the ethanol is 10 to 1:1, and the concentration of the sodium hydroxide in the mixed solution is 0.01 to 0.1mol/L.
In a preferred embodiment of the present invention, in step (5), the concentration of dopamine hydrochloride in the mixed solution is 10-50mg/mL, and the concentration of tris (hydroxymethyl) aminomethane is 1-10mmol/mL.
The third technical scheme adopted by the invention for solving the technical problems is as follows: provides a magnesium battery, which adopts the nano carbon layer containing oxygen defects to coat a titanium dioxide electrode.
In a preferred embodiment of the invention, the carbon nano-layer coated titanium dioxide electrode containing oxygen defects is used as a positive electrode, the magnesium sheet is used as a negative electrode, 0.4M MgPhCl/THF is used as electrolyte, glass fiber is used as a diaphragm, and the assembly process of the battery is in an argon atmosphere.
Compared with the background technology, the technical scheme has the following advantages:
1. the preparation method directly grows the titanium dioxide with oxygen defects and uniform nano carbon coating on the titanium foil, does not need the chemical vapor deposition and other processes with high technical requirements to realize the introduction of the nano carbon layer, and can realize the controllable growth of the nano carbon layer by controlling the concentration of the solution chemically treated by dopamine, the soaking time and the like; meanwhile, the electrode does not need a complicated traditional process to coat the electrode, so that the production process of the magnesium battery anode is greatly simplified;
2. the surface of the electrode prepared by the invention has a three-dimensional nanorod array structure, enough pores in the structure can ensure that electrolyte is fully contacted with active substances so as to expose more active sites and improve the rate performance of a battery, and meanwhile, the uniform nano carbon coating and oxygen defects are introduced into the electrode so as to effectively improve the electronic conductivity and the ionic conductivity of the active electrode and improve the diffusion dynamics of magnesium ions in the active substances, so that titanium dioxide can realize higher specific discharge capacity and long cycle life;
3. the electrode is directly used as the anode of the magnesium battery, so that the energy density and the electrochemical performance of the magnesium battery can be effectively improved, and the electrode is non-toxic, harmless, safe and environment-friendly;
4. according to the invention, no binder or conductive agent is additionally introduced, the energy density of the whole battery can be effectively improved, and due to the extremely strong chemical bonding force, the titanium dioxide growing on the surface of the titanium foil cannot fall off in the circulating process, so that the stable circulation for a long time can be maintained.
Drawings
Fig. 1 is an XRD spectrum of the electrode active material layer of example 1;
FIG. 2 is an EPR spectrum of the electrode active material layer of example 1;
FIG. 3 is a scanning electron micrograph of an electrode active material layer of example 1;
FIG. 4 is a high-resolution transmission electron micrograph of an electrode active material layer of example 1;
fig. 5 is a charge-discharge graph of the magnesium battery of example 1.
Detailed Description
Example 1
The preparation method of the oxygen-defect-containing nano carbon layer-coated titanium dioxide electrode comprises the following steps:
0.2g of sodium hydroxide was weighed out and dissolved in 100mL of a mixed solution of deionized water and ethanol (volume ratio V) Water (W) ：V Ethanol = 6:1); putting the titanium foil into the mixed solution, and reacting for 15h at 180 ℃ to obtain a reaction intermediate; soaking the reaction intermediate in dilute hydrochloric acid for 4h, washing the reaction intermediate with water, and naturally airing; after the reaction intermediate is completely dried, calcining the reaction intermediate in a muffle furnace at a high temperature of 400 ℃ for 6 hours to obtain a titanium dioxide electrode; soaking the obtained titanium dioxide electrode in a mixed solution of 20mg/mL dopamine hydrochloride and 2mg/mL tris (hydroxymethyl) aminomethane for 5 hours; and calcining the soaked electrode at high temperature of 800 ℃ for 3h in an inert atmosphere to obtain the oxygen-defect-containing nano carbon layer coated titanium dioxide electrode.
The electrode of the embodiment consists of a titanium current collector and an active material layer, wherein the active material layer directly grows on the surface of the titanium current collector and comprises a three-dimensional structure formed by stacking a plurality of nanorod arrays, and ion transmission pore passages are formed among the three-dimensional structures; the nano rod is made of titanium dioxide with oxygen defects, and the surface of the nano rod is coated with a nano carbon layer with controllable growth. It can be seen in figure 2 that it has a distinct oxygen vacancy signal peak. It can be seen in fig. 3 that it has a three-dimensional nanorod array structure. It can be seen in fig. 4 that it has a uniform coating of nanocarbon.
The electrode of the embodiment is used as a positive electrode, the magnesium sheet is used as a negative electrode, 0.4M MgPhCl/THF is used as electrolyte, glass fiber is used as a diaphragm, and the magnesium battery is assembled in an argon atmosphere in the whole process. Fig. 5 is a charge-discharge curve diagram of the magnesium battery of the present embodiment, which shows that the magnesium battery has high specific discharge capacity and excellent cycle performance.
Example 2
This example differs from example 1 in that;
0.3g of sodium hydroxide was weighed out and dissolved in 100mL of deionized waterMixed solution of water and ethanol (volume ratio V) Water (I) ：V Ethanol =3: 1) The preparation method comprises the following steps of (1) performing; putting the titanium foil into the mixed solution, and reacting for 20 hours at 120 ℃ to obtain a reaction intermediate; soaking the reaction intermediate in dilute hydrochloric acid for 15 hours, washing the reaction intermediate with water, and naturally airing; after the reaction intermediate is completely dried, calcining the reaction intermediate in a muffle furnace at a high temperature of 600 ℃ for 7 hours to obtain a titanium dioxide electrode; soaking the obtained titanium dioxide electrode in 10mg/mL dopamine hydrochloride and 5mg/mL tris (hydroxymethyl) aminomethane for 10h; and calcining the soaked electrode at high temperature of 600 ℃ for 4 hours in an inert atmosphere to obtain the oxygen-defect-containing nano carbon layer coated titanium dioxide electrode.
Example 3
This example differs from example 1 in that;
0.1g of sodium hydroxide was weighed and dissolved in 100mL of a mixed solution of deionized water and ethanol (volume ratio V) Water (I) ：V Ethanol = 1:1); putting the titanium foil into the mixed solution, and reacting for 16 hours at 210 ℃ to obtain a reaction intermediate; soaking the reaction intermediate in dilute hydrochloric acid for 5h, washing the reaction intermediate with water, and naturally airing; after the reaction intermediate is completely dried, calcining the reaction intermediate in a muffle furnace at a high temperature of 400 ℃ for 8 hours to obtain a titanium dioxide electrode; soaking the obtained titanium dioxide electrode in 50mg/mL dopamine hydrochloride and 1mg/mL tris (hydroxymethyl) aminomethane for 5h; and calcining the soaked electrode at high temperature in an inert atmosphere, wherein the calcining temperature is 700 ℃, and the calcining time is 2 hours, so as to obtain the oxygen-defect-containing nano carbon layer coated titanium dioxide electrode.
Comparative example 1
This comparative example differs from example 1 in that;
0.2g of sodium hydroxide was weighed out and dissolved in 100mL of a mixed solution of deionized water and ethanol (volume ratio V) Water (W) ：V Ethanol = 6:1); putting the titanium foil into the mixed solution, and reacting for 15h at 180 ℃ to obtain a reaction intermediate; soaking the reaction intermediate in dilute hydrochloric acid for 4 hours, washing the reaction intermediate with water, and naturally airing; the intermediate is completely driedAnd then, calcining the titanium dioxide electrode at a high temperature of 400 ℃ in a muffle furnace for 6 hours to obtain the titanium dioxide electrode.
Comparative example 2
This comparative example differs from example 1 in that;
0.3g of sodium hydroxide was weighed out and dissolved in 100mL of a mixed solution of deionized water and ethanol (volume ratio V) Water (W) ：V Ethanol =3: 1) Performing the following steps; putting the titanium foil into the mixed solution, and reacting for 20 hours at 120 ℃ to obtain a reaction intermediate; soaking the reaction intermediate in dilute hydrochloric acid for 15h, washing the reaction intermediate with water, and naturally airing; and after the reaction intermediate is completely dried, calcining the reaction intermediate in a muffle furnace at the high temperature of 600 ℃ for 7 hours to obtain the titanium dioxide electrode.
Comparative example 3
This comparative example differs from example 1 in that;
0.1g of sodium hydroxide was weighed and dissolved in 100mL of a mixed solution of deionized water and ethanol (volume ratio V) Water (W) ：V Ethanol = 1:1); putting the titanium foil into the mixed solution, and reacting for 16h at 210 ℃ to obtain a reaction intermediate; soaking the reaction intermediate in dilute hydrochloric acid for 5 hours, washing the reaction intermediate with water, and naturally airing; and after the reaction intermediate is completely dried, calcining the reaction intermediate in a muffle furnace at the high temperature of 400 ℃ for 8 hours to obtain the titanium dioxide electrode.
Comparative example 4
This comparative example differs from example 1 in that;
the active material of the positive electrode of the comparative example was commercialized nano TiO 2 Mixing with conductive agent and adhesive in proportion, adding N-methyl pyrrolidone as slurry, coating the slurry on titanium foil, and drying at 80-180 deg.C to obtain commercial TiO 2 And (4) a positive electrode.
The electrode is used as a positive electrode and assembled with a magnesium negative electrode to form a magnesium battery, and the charge and discharge performance test is carried out, wherein the results are as follows:
TABLE 1
Figure BDA0003757912700000071
TABLE 2
Figure BDA0003757912700000072
Figure BDA0003757912700000081
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (10)

1. A nano carbon layer coated titanium dioxide electrode containing oxygen defects is characterized in that: consists of a current collector and an active material layer; the current collector is a titanium foil; the active material layer grows on the surface of the current collector and comprises a three-dimensional structure formed by stacking a plurality of nanorod arrays, and ion transmission pore canals are formed among the three-dimensional structures; the nano rod is made of titanium dioxide with oxygen defects, and the surface of the nano rod is coated with a nano carbon layer with controllable growth.
2. The oxygen-defect-containing nano carbon layer-coated titanium dioxide electrode as claimed in claim 1, wherein: the nano carbon layer is 5-50nm thick and is uniformly and continuously arranged on the surface of the titanium dioxide.
3. The oxygen-defect-containing nano carbon layer-coated titanium dioxide electrode as claimed in claim 1, wherein: the width of the nano rod is 50-100nm, and the length is 0.5-10 μm.
4. The oxygen-defect-containing nano carbon layer-coated titanium dioxide electrode as claimed in claim 1, wherein: the thickness of the active material layer is 10-100 μm.
5. The oxygen-defect-containing nano carbon layer coated titanium dioxide electrode as claimed in claim 1, wherein: the nano carbon layer is formed by infiltrating the nano rods with a mixed solution of dopamine hydrochloride and tris (hydroxymethyl) aminomethane and then calcining and carbonizing the nano carbon layer.
6. A preparation method of a nano carbon layer coated titanium dioxide electrode containing oxygen defects is characterized by comprising the following steps: the method comprises the following steps:
(1) Dissolving sodium hydroxide in a mixed solution of deionized water and ethanol;
(2) Putting the titanium foil into the mixed solution, and reacting for 2-20h at 120-220 ℃ to obtain a reaction intermediate;
(3) Soaking the reaction intermediate in dilute hydrochloric acid for 1-20h, then washing with water and naturally airing;
(4) After the reaction intermediate is completely dried, calcining the reaction intermediate in a muffle furnace at the high temperature of 200-800 ℃ for 1-8h to obtain a titanium dioxide electrode with a three-dimensional structure formed by stacking a nanorod array;
(5) Soaking the obtained titanium dioxide electrode in a mixed solution of dopamine hydrochloride and tris (hydroxymethyl) aminomethane for 1-20h until the mixed solution fills a three-dimensional structure gap to obtain a polydopamine-coated titanium dioxide electrode;
(6) And (3) calcining the soaked electrode at high temperature in an argon or nitrogen atmosphere, wherein the calcining temperature is 200-800 ℃, and the calcining time is 1-5h, so as to obtain the oxygen defect-containing carbon-coated titanium dioxide electrode.
7. The method of claim 6, wherein: in the step (1), the volume ratio of the deionized water to the ethanol is 10-1:1, and the concentration of the sodium hydroxide in the mixed solution is 0.01-0.1mol/L.
8. The method of claim 6, wherein: in the step (5), the concentration of dopamine hydrochloride in the mixed solution is 10-50mg/mL, and the concentration of tris (hydroxymethyl) aminomethane is 1-10mmol/mL.
9. A magnesium battery, characterized in that: coating a titanium dioxide electrode with an oxygen-deficient nanocarbon layer according to any one of claims 1 to 5.
10. A magnesium battery according to claim 9, wherein: the method is characterized in that a nano carbon layer coated titanium dioxide electrode with oxygen defects is used as a positive electrode, a magnesium sheet is used as a negative electrode, 0.4M MgPhCl/THF is used as electrolyte, glass fibers are used as a diaphragm, and the battery is assembled in an argon atmosphere.
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