CN107934965B - Ti3C2-Co(OH)(CO3)0.5Process for preparing nano composite material - Google Patents

Ti3C2-Co(OH)(CO3)0.5Process for preparing nano composite material Download PDF

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CN107934965B
CN107934965B CN201711350994.XA CN201711350994A CN107934965B CN 107934965 B CN107934965 B CN 107934965B CN 201711350994 A CN201711350994 A CN 201711350994A CN 107934965 B CN107934965 B CN 107934965B
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武文玲
卫丹
朱建锋
崔云
方园
王芬
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Shaanxi University of Science and Technology
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Abstract

Ti3C2‑Co(OH)(CO3)0.5The preparation of the nano composite material is carried out by selectively etching off ternary Ti in 40 wt% HF solution3AlC2Al layer of ceramic powder to form two-dimensional layered Ti3C2A nanomaterial; then, with two-dimensional Ti3C2Nano material as matrix and Co (NO)3)2·6H2O is a source of cobalt, CO (NH)2)2Uniformly stirring the precipitant, and carrying out in-situ growth on the mixed solution at 80-85 ℃ by a hydrothermal method to successfully prepare Ti with various shapes3C2@Co(OH)(CO3)0.5A nanocomposite; and assembling it into a supercapacitor of three-electrode system, Ti3C2‑Co(OH)(CO3)0.5The electrochemical performance is good; the method has simple experimental process, low cost, environmental protection, and high content of Co (OH) (CO)3)0.5The morphology is easy to control and is Ti3C2‑Co(OH)(CO3)0.5Lays a foundation for the application of super capacitors and lithium ion batteries.

Description

Ti3C2-Co(OH)(CO3)0.5Process for preparing nano composite material
Technical Field
The invention belongs to the technical field of preparation of nano functional materials and electrochemical energy storage materials, and particularly relates to Ti3C2-Co(OH)(CO3)0.5A method for preparing a nanocomposite.
Background
Novel two-dimensional material MXene is transition gold with graphene-like structureOf carbonitrides or carbides, e.g. Ti3C2、Ti2C and the like. Ti3C2Removal of MAX phase Ti from nano material by HF selective etching3AlC2The Al layer element in the MAX structure is prepared and can be kept unchanged. Two-dimensional carbide Ti3C2Good stability, larger specific surface area, high bending strength and elastic modulus, and excellent electrical property and conductivity, which indicates that the material can be used as an ideal matrix of a composite material, and has wide application prospects in the fields of electrochemistry, composite material reinforcement and the like.
Naguib et al acid etch Ti3AlC2And after the aluminum alloy is completely soaked in hydrofluoric acid for a certain time at room temperature, the Al atomic layer is completely stripped.
Maria et al press on Ti3C2: conductive agent: the mass ratio of the adhesive is 85 percent to 10 percent to 5 percent, and Ti is treated by adopting a three-electrode asymmetric system in KOH solution3C2The electrochemical performance of (2) is characterized. The experimental result shows that Ti3C2The specific volume capacity of the catalyst can reach 340F/cm in KOH solution3And the interlayer spacing increases.
Sun et al general description of Ti3C2As a lithium ion electrode cathode material, a test result shows that the capacity of the lithium ion battery can reach 123.6mAh/g under the multiplying power of 1C, and the coulombic efficiency is about 47%. However, Ti3C2The theoretical specific capacity is small, so that the electrochemical performance of the lithium ion battery is poor, and the application of MXene group in the energy storage fields of super capacitors, lithium ion batteries and the like is yet to be further researched.
Basic cobalt carbonate Co (OH) (CO)3)0.5Is to prepare nano Co3O4Good precursors for materials have therefore gained much attention in recent years. Basic cobalt carbonate is easy to decompose by heating, but the decomposition product has few impurities, so the basic cobalt carbonate is very suitable for processing and manufacturing various cobalt materials and is commonly used as an additive of electronic materials and magnetic materials. In recent years, research on the crystal structure, thermal stability, surface properties and the like of the basic carbonate has been advanced. However, studies on their electrochemical propertiesIt has not yet been matured.
Zhou W.J. et al electrochemically deposit Co (OH) as an active material2Directly deposited on a substrate and tested as a working electrode of a super capacitor, and the specific capacitance is up to 1084F/g.
Searching the literature, and finding that Co (OH) (CO) has not been utilized to date3)0.5To improve Ti3C2The electrochemical performance of (2). The invention uses two-dimensional Ti with good conductivity and stable structure3C2Ceramic powder as matrix and Co (NO)3)2·6H2O is a source of cobalt, CO (NH)2)2Is a precipitator, PVP is used as a structure directing agent, Ti is successfully prepared by in-situ growth at 80-85 ℃ by a hydrothermal method3C2@Co(OH)(CO3)0.5A nanocomposite material. And assembling it into a supercapacitor of three-electrode system, Ti3C2-Co(OH)(CO3)0.5The electrochemical performance is good, the experimental process is simple, the product appearance is controllable, the method is safe and environment-friendly, and a foundation is laid for the application of the method in the energy storage fields of lithium ion batteries, super capacitors and the like.
Disclosure of Invention
In order to overcome the above-mentioned drawbacks of the prior art, the present invention is directed to providing a Ti3C2-Co(OH)(CO3)0.5The preparation method of the nano composite material utilizes a hydrothermal method to grow Co (OH) (CO) in situ3)0.5Preparing Ti with various shapes3C2-Co(OH)(CO3)0.5The method has simple experimental process, low cost, environmental protection, and high performance of Co (OH) (CO)3)0.5The shape is easy to control, and Ti is enlarged3C2The specific surface area of the electrode improves the electrode material of the super capacitor.
In order to achieve the purpose, the invention adopts the technical scheme that:
ti3C2-Co(OH)(CO3)0.5A method for preparing a nanocomposite comprising the steps of:
step (ii) ofFirstly, preparing ternary Ti3AlC2Ceramic powder;
step two, preparing two-dimensional layered Ti3C2A nanomaterial;
step three, Ti3C2-Co(OH)(CO3)0.5Preparing a nano composite material;
first, 145.5-1164mg of Co (NO)3)2·6H2O and the two-dimensional layered Ti obtained in the step (2)3C2Dissolving 200mg of nano powder in ultrapure water, and sequentially adding 100-800mg of CO (NH) under magnetic stirring2)2And 200 and 1600g PVP are continuously stirred for 0.5 to 2 hours to obtain mixed solution; secondly, transferring the mixed solution with the volume fraction of 75% into a polytetrafluoroethylene lining of a 100ml hydrothermal reaction kettle, heating the assembled hydrothermal reaction kettle to 80-85 ℃, and preserving the heat for 6-12 h; then, the product naturally cooled to room temperature is respectively centrifugally separated and cleaned for 3 times by sequentially using ultrapure water and absolute ethyl alcohol, and is centrifuged for 3-5min at the speed of 4000-; finally, drying in a vacuum drying oven at 40 ℃ for 12-24h to obtain the required Ti3C2@Co(OH)(CO3)0.5A nanocomposite material.
Step four, Ti3C2-Co(OH)(CO3)0.5Preparing an electrode;
firstly, the foamed nickel is cut into 1 x 2cm2A rectangle with a size of 160-200mg of active substances, namely Ti obtained in the third step3C2@Co(OH)(CO3)0.5Grinding the nano powder, 20-30mg of conductive acetylene black and 1-10mg of polyvinylidene fluoride in an agate mortar for 1-2 h; secondly, sucking 300 mu L of NMP by a liquid transfer gun, grinding uniformly, then evenly dripping the slurry on the cut foam nickel, and drying the dripped foam nickel for 12-24h in a vacuum drying oven at the temperature of 60-80 ℃; thirdly, keeping the pressure of the prepared electrode slice at 15-20Mpa for 1min under a tablet press to obtain Ti3C2@Co(OH)(CO3)0.5And an electrode.
The first step is to prepare the ternary layered Ti3AlC2The ceramic powder specifically comprises: first, according to the molar ratio Ti: al: 1.0 of TiC: 1.2: 2.0 mixing the three raw materials; secondly, placing the three raw materials in a ball milling tank, taking alumina balls as a grinding medium, taking absolute ethyl alcohol as a ball milling auxiliary agent, setting the rotating speed of the ball mill at 900 revolutions per minute, and taking the raw materials as balls according to the mass ratio: material preparation: ethanol ═ 3.0: 1.0: 1.0, performing common ball milling for 1h to obtain uniform powder, and drying the powder in a constant-temperature drying oven at 40 ℃; then, the dried mixed material is placed in a corundum crucible, a vacuum pressureless sintering method is adopted, the temperature is increased to 1350 ℃ at the heating rate of 8 ℃/min, the temperature is kept for 1h, and the mixture is cooled to room temperature along with the furnace to obtain high-purity Ti3AlC2Ceramic powder.
Finally, to Ti3AlC2Carrying out wet high-energy ball milling on the ceramic powder for 3 hours, once every 30 minutes, rotating at the rotating speed of 400r/min, wherein the mass ratio of the steel balls to the ceramic powder is 10:1, and sieving the ground powder to obtain ternary Ti with the particle size of less than 38 mu m3AlC2Ceramic powder.
Step two is to prepare two-dimensional layered Ti3C2The nano material specifically comprises: taking 5g of Ti obtained in the step (one)3AlC2Slowly immersing the ceramic powder in 100mL of 40 wt% hydrofluoric acid solution until no bubbles are generated, magnetically stirring the ceramic powder at room temperature for 48 hours at the rotating speed of 1200r/min, centrifugally cleaning the corrosion product by deionized water until the pH value of a supernatant is about 5-6, centrifuging the corrosion product by absolute ethyl alcohol for 4 times, and finally vacuum drying black precipitate at 40 ℃ for 24 hours to obtain the two-dimensional layered Ti3C2And (3) nano powder.
And (3) product verification:
using a three-electrode system with Ti3C2@Co(OH)(CO3)0.5The electrode is used as a working electrode, a platinum sheet is used as a counter electrode, silver and silver chloride are used as reference electrodes, and Ti is tested by using the electrochemical workstation CHI660E in Shanghai Chen Hua under 6M KOH electrolyte3C2@Co(OH)(CO3)0.5The electrochemical performance of the electrode, such as cyclic voltammetry curve, constant current charging and discharging, and alternating current impedance. Ti3C2-Co(OH)(CO3)0.5The electrochemical performance is good, the CV curve graph is close to a regular rectangle, and the symmetry is good; circulation curveThe formed area increases with the increase of the scanning rate, but the rough shape of the pattern is basically unchanged, and good rate performance is shown.
The invention has the beneficial effects that:
1. the invention first selectively etches off ternary Ti in HF solution with concentration of 40 wt%3AlC2Al layer of ceramic powder to form two-dimensional layered Ti3C2And (3) nano materials. Then, with two-dimensional Ti3C2Nano material as matrix and Co (NO)3)2·6H2O is a source of cobalt, CO (NH)2)2Uniformly stirring the precipitator, and then carrying out in-situ growth on the mixed solution at 80-85 ℃ by a hydrothermal method to successfully prepare Ti3C2@Co(OH)(CO3)0.5A nanocomposite material. And the three-electrode super capacitor is assembled by using 6M KOH solution as electrolyte and Ti3C2-Co(OH)(CO3)0.5As a working electrode, a platinum electrode as a counter electrode and a silver/silver chloride electrode as a reference electrode to perform cyclic voltammetry, and Ti3C2-Co(OH)(CO3)0.5The electrochemical performance is good, the experimental process is simple, the product appearance is controllable, the method is safe and environment-friendly, and a foundation is laid for the application of the method in the energy storage fields of lithium ion batteries, super capacitors and the like.
2. The prepared Ti with various shapes3C2-Co(OH)(CO3)0.5The nanocomposite serving as an active electrode of a supercapacitor is tested on a CHI660E electrochemical workstation, and shows good electrochemical performance, namely Ti3C2-Co(OH)(CO3)0.5Lays a foundation for the application of super capacitors and lithium ion batteries.
Drawings
FIG. 1 is Ti3C2-Co(OH)(CO3)0.5The XRD patterns of the nano composite material are shown in the following four curves of a, b, c and d, which are the XRD patterns of the first, second, third and fourth examples.
FIG. 2 is Ti3C2-Co(OH)(CO3)0.5SEM images of the nanocomposite, wherein a, b, c, d are SEM images of examples one, two, three, and four, respectively.
FIG. 3 shows example III3C2-Co(OH)(CO3)0.5Cyclic voltammograms of nanocomposites at different scan rates under a three-electrode system.
Detailed Description
The present invention will be described in further detail with reference to the following drawings and examples.
Example one
The embodiment comprises the following steps:
step one, ternary Ti3AlC2Preparing ceramic powder;
preparation of ternary layered Ti according to the method of patent ZL201310497696.93AlC2Ceramic powder: first, according to the molar ratio Ti: al: 1.0 part of TiC: 1.2: 2.0 mixing the three raw materials; secondly, placing the three raw materials in a ball milling tank, taking alumina balls as a grinding medium, taking absolute ethyl alcohol as a ball milling auxiliary agent, setting the rotating speed of the ball mill at 900 revolutions per minute, and taking the raw materials as balls according to the mass ratio: material preparation: ethanol ═ 3.0: 1.0: 1.0, performing common ball milling for 1h to obtain uniform powder, and drying the powder in a constant-temperature drying oven at 40 ℃; then, the dried mixed material is placed in a corundum crucible, a vacuum pressureless sintering method is adopted, the temperature is increased to 1350 ℃ at the heating rate of 8 ℃/min, the temperature is kept for 1h, and the mixture is cooled to room temperature along with the furnace to obtain high-purity Ti3AlC2Ceramic powder.
Finally, to Ti3AlC2Carrying out wet high-energy ball milling on the ceramic powder for 3 hours, once every 30 minutes, rotating at the rotating speed of 400r/min, wherein the mass ratio of the steel balls to the ceramic powder is 10:1, and sieving the ground powder to obtain Ti with the particle size of less than 38 mu m3AlC2Ceramic powder.
Step two, two-dimensional layered Ti3C2Preparing a nano material;
preparation of two-dimensional layered Ti according to the method of patent 201410812056.73C2Taking 5g of Ti obtained in the step (I)3AlC2Slowly immersing the ceramic powder in 100mL of 40 wt% hydrofluoric acid solution until no bubbles are generated, magnetically stirring the ceramic powder at room temperature for 48 hours at the rotating speed of 1200r/min, centrifugally cleaning the corrosion product by using deionized water until the pH value of the supernatant is about 5-6, and centrifuging the corrosion product by using absolute ethyl alcohol for 4 times. Finally, vacuum drying the black precipitate for 24 hours at 40 ℃ to obtain the two-dimensional layered Ti3C2And (3) nano powder.
Step three, Ti3C2-Co(OH)(CO3)0.5Preparing a nano composite material;
first, 1164mg of Co (NO)3)2·6H2O and Ti obtained in the step (2)3C2Dissolving 200mg of nano powder in ultrapure water, and adding 800mg of CO (NH) in sequence under magnetic stirring2)2Continuously stirring the mixed solution and 1600mg of PVP for 2h to obtain mixed solution; secondly, transferring the mixed solution with the volume fraction of 75% into a polytetrafluoroethylene lining of a 100ml hydrothermal reaction kettle, heating the assembled hydrothermal reaction kettle to 82 ℃, and preserving the heat for 8 hours; then, the product naturally cooled to room temperature is respectively centrifugally separated and cleaned for 3 times by sequentially using ultrapure water and absolute ethyl alcohol, and is centrifuged for 3-5min at the speed of 4000-; finally, drying the Ti in a vacuum drying oven at 40 ℃ for 24 hours to obtain the required Ti3C2@Co(OH)(CO3)0.5A nanocomposite material. As can be seen from the curve a in fig. 1, in addition to the characteristic peaks of Ti3C2 corresponding to the (111), (200), (220) crystal planes at 2 θ 36 °, 42 °, 62 °, CO (oh) (CO) at 48-0083 in the PDF standard card at 2 θ 18 °, 25 °, 34 °, 18 °, 25 °, 36 °3)0.5Diffraction peaks of (020), (111), and (221) crystal planes of (A). Shows that Ti is successfully prepared by a hydrothermal method3C2@ precursor Co (OH) (CO)3)0.5A composite material. As can be seen from the a diagram of FIG. 2, Co (OH) (CO) is present in the reaction system due to too much loading3)0.5At Ti3C2The surface of the material is provided with a thicker coating layer, Co (OH) (CO)3)0.5Is in a nano sheet shape and self-assembled into a flower-shaped image.
Step four, Ti3C2-Co(OH)(CO3)0.5Preparing an electrode;
firstly, the foamed nickel is cut into 1 x 2cm2The size of the rectangle is 200mg of active substance, namely Ti obtained in the third step3C2@Co(OH)(CO3)0.5Grinding the nano powder, 20mg of conductive acetylene black and 1mg of polyvinylidene fluoride in an agate mortar for 1-2 h; secondly, sucking 300 mu L of NMP by a liquid transfer gun, grinding uniformly, then evenly dripping the slurry on the cut foam nickel, and drying the dripped foam nickel in a vacuum drying oven for 24 hours at 60 ℃; thirdly, keeping the pressure of the prepared electrode slice at 15MPa for 1min under a tablet press to obtain Ti3C2@Co(OH)(CO3)0.5And an electrode.
Finally, a three-electrode system is adopted, and Ti is used3C2@Co(OH)(CO3)0.5The electrode is used as a working electrode, a platinum sheet is used as a counter electrode, silver and silver chloride are used as reference electrodes, and Ti is tested by using the electrochemical workstation CHI660E in Shanghai Chen Hua under 6M KOH electrolyte3C2@Co(OH)(CO3)0.5The electrochemical performance of the electrode, such as cyclic voltammetry curve, constant current charging and discharging, and alternating current impedance.
Example two
The embodiment comprises the following steps:
step one, ternary Ti3AlC2Preparing ceramic powder;
preparation of ternary layered Ti according to the method of patent ZL201310497696.93AlC2Ceramic powder: first, according to the molar ratio Ti: al: 1.0 part of TiC: 1.2: 2.0 mixing the three raw materials; secondly, placing the three raw materials in a ball milling tank, taking alumina balls as a grinding medium, taking absolute ethyl alcohol as a ball milling auxiliary agent, setting the rotating speed of the ball mill at 900 revolutions per minute, and taking the raw materials as balls according to the mass ratio: material preparation: ethanol ═ 3.0: 1.0: 1.0, performing common ball milling for 1h to obtain uniform powder, and drying the powder in a constant-temperature drying oven at 40 ℃; then, the dried mixed material is placed in a corundum crucible, a vacuum pressureless sintering method is adopted, the temperature is increased to 1350 ℃ at the heating rate of 8 ℃/min, the temperature is kept for 1h, and the mixture is cooled to room temperature along with the furnace to obtain high-purity Ti3AlC2Ceramic powder.
Finally, to Ti3AlC2Carrying out wet high-energy ball milling on the ceramic powder for 3 hours, once every 30 minutes, rotating at the rotating speed of 400r/min, wherein the mass ratio of the steel balls to the ceramic powder is 10:1, and sieving the ground powder to obtain Ti with the particle size of less than 38 mu m3AlC2Ceramic powder.
Step two, two-dimensional layered Ti3C2Preparing a nano material;
preparation of two-dimensional layered Ti according to the method of patent 201410812056.73C2Taking 5g of Ti obtained in the step (I)3AlC2Slowly immersing the ceramic powder in 100mL of 40 wt% hydrofluoric acid solution until no bubbles are generated, magnetically stirring the ceramic powder at room temperature for 48 hours at the rotating speed of 1200r/min, centrifugally cleaning the corrosion product by using deionized water until the pH value of the supernatant is about 5-6, and centrifuging the corrosion product by using absolute ethyl alcohol for 4 times. Finally, vacuum drying the black precipitate for 24 hours at 40 ℃ to obtain the two-dimensional layered Ti3C2And (3) nano powder.
Step three, Ti3C2-Co(OH)(CO3)0.5Preparing a nano composite material;
first, 727.6mg of Co (NO)3)2·6H2O and Ti obtained in the step (2)3C2Dissolving 200mg of nano powder in ultrapure water, and sequentially adding 500mg of CO (NH) under magnetic stirring2)2Continuously stirring the mixed solution and 1000mg of PVP for 2 hours to obtain mixed solution; secondly, transferring the mixed solution with the volume fraction of 75% into a polytetrafluoroethylene lining of a 100ml hydrothermal reaction kettle, heating the assembled hydrothermal reaction kettle to 82 ℃, and preserving the heat for 8 hours; then, the product naturally cooled to room temperature is respectively centrifugally separated and cleaned for 3 times by sequentially using ultrapure water and absolute ethyl alcohol, and is centrifuged for 3-5min at the speed of 4000-; finally, drying the Ti in a vacuum drying oven at 40 ℃ for 24 hours to obtain the required Ti3C2@Co(OH)(CO3)0.5A nanocomposite material. As can be seen from the curve b in fig. 1, in addition to the characteristic peaks of Ti3C2 corresponding to the (111), (200) and (220) crystal planes at 2 θ 36 °, 42 ° and 62 °, CO (oh) (CO) with PDF standard card number 48-0083 at 2 θ 18 °, 25 ° and 34 ° are shown3)0.5Diffraction peaks of (020), (111), and (221) crystal planes of (A). Shows that Ti is successfully prepared by a hydrothermal method3C2@ precursor Co (OH) (CO)3)0.5A composite material. As can be seen from the b-diagram of FIG. 2, Co (OH) (CO) was still supported in the reaction system in a large amount3)0.5At Ti3C2The surface of the material is provided with a thicker coating layer, Co (OH) (CO)3)0.5Is in a nanowire shape.
Step four, Ti3C2-Co(OH)(CO3)0.5Preparing an electrode;
firstly, the foamed nickel is cut into 1 x 2cm2The size of the rectangle is 200mg of active substance, namely Ti obtained in the third step3C2@Co(OH)(CO3)0.5Grinding the nano powder, 2mg of conductive acetylene black and 1mg of polyvinylidene fluoride in an agate mortar for 1-2 h; secondly, sucking 300 mu L of NMP by a liquid transfer gun, grinding uniformly, then evenly dripping the slurry on the cut foam nickel, and drying the dripped foam nickel in a vacuum drying oven for 24 hours at 60 ℃; thirdly, keeping the pressure of the prepared electrode slice at 15MPa for 1min under a tablet press to obtain Ti3C2@Co(OH)(CO3)0.5And an electrode.
Finally, a three-electrode system is adopted, and Ti is used3C2@Co(OH)(CO3)0.5The electrode was used as the working electrode, the platinum sheet as the counter electrode, the silver/silver chloride as the reference electrode, and Ti was tested using the Shanghai Hua CHI660E electrochemical workstation in 6M KOH electrolyte3C2@Co(OH)(CO3)0.5The electrochemical performance of the electrode, such as cyclic voltammetry curve, constant current charging and discharging, and alternating current impedance.
EXAMPLE III
The embodiment comprises the following steps:
step one, ternary Ti3AlC2Preparing ceramic powder;
preparation of ternary layered Ti according to the method of patent ZL201310497696.93AlC2Ceramic powder: first, according to the molar ratio Ti: al: 1.0 part of TiC: 1.2: 2.0 mixing the three raw materialsCombining; secondly, placing the three raw materials in a ball milling tank, taking alumina balls as a grinding medium, taking absolute ethyl alcohol as a ball milling auxiliary agent, setting the rotating speed of the ball mill at 900 revolutions per minute, and taking the raw materials as balls according to the mass ratio: material preparation: ethanol ═ 3.0: 1.0: 1.0, performing common ball milling for 1h to obtain uniform powder, and drying the powder in a constant-temperature drying oven at 40 ℃; then, the dried mixed material is placed in a corundum crucible, a vacuum pressureless sintering method is adopted, the temperature is increased to 1350 ℃ at the heating rate of 8 ℃/min, the temperature is kept for 1h, and the mixture is cooled to room temperature along with the furnace to obtain high-purity Ti3AlC2Ceramic powder.
Finally, to Ti3AlC2Carrying out wet high-energy ball milling on the ceramic powder for 3 hours, once every 30 minutes, rotating at the rotating speed of 400r/min, wherein the mass ratio of the steel balls to the ceramic powder is 10:1, and sieving the ground powder to obtain Ti with the particle size of less than 38 mu m3AlC2Ceramic powder.
Step two, two-dimensional layered Ti3C2Preparing a nano material;
preparation of two-dimensional layered Ti according to the method of patent 201410812056.73C2Taking 5g of Ti obtained in the step (I)3AlC2Slowly immersing the ceramic powder in 100mL of 40 wt% hydrofluoric acid solution until no bubbles are generated, magnetically stirring the ceramic powder at room temperature for 48 hours at the rotating speed of 1200r/min, centrifugally cleaning the corrosion product by using deionized water until the pH value of the supernatant is about 5-6, and centrifuging the corrosion product by using absolute ethyl alcohol for 4 times. Finally, vacuum drying the black precipitate for 24 hours at 40 ℃ to obtain the two-dimensional layered Ti3C2And (3) nano powder.
Step three, Ti3C2-Co(OH)(CO3)0.5Preparing a nano composite material;
first, 291.0mg of Co (NO)3)2·6H2O and Ti obtained in the step (2)3C2Dissolving nanometer powder 200mg in ultrapure water, adding CO (NH) 200mg under magnetic stirring2)2Continuously stirring the mixed solution and 400mg of PVP for 2 hours to obtain mixed solution; secondly, transferring the mixed solution with the volume fraction of 75 percent into a polytetrafluoroethylene lining of a 100ml hydrothermal reaction kettle, and lifting the assembled hydrothermal reaction kettleHeating to 82 ℃ and preserving the temperature for 8 h; then, the product naturally cooled to room temperature is respectively centrifugally separated and cleaned for 3 times by sequentially using ultrapure water and absolute ethyl alcohol, and is centrifuged for 3-5min at the speed of 4000-; finally, drying the Ti in a vacuum drying oven at 40 ℃ for 24 hours to obtain the required Ti3C2@Co(OH)(CO3)0.5A nanocomposite material. As can be seen from the c-curve of fig. 1, when 2 θ is 36 °, 42 °, 62 ° respectively corresponds to Ti of the (111), (200), (220) crystal planes3C2In addition to the characteristic peaks, the peaks are also Co (OH) (CO) with 2 theta being 18 degrees, 25 degrees and 34 degrees corresponding to PDF standard card numbers of 48-00833)0.5Diffraction peaks of (020), (111), and (221) crystal planes of (A). Shows that Ti is successfully prepared by a hydrothermal method3C2@ precursor Co (OH) (CO)3)0.5A composite material. Ti is clearly seen from the c diagram of FIG. 23C2Concertina structure of Co (OH) (CO)3)0.5The shape of the nano-wire is changed into a honeycomb shape and finally changed into nano-particles distributed on Ti3C2The sheet surface and the layers. Ti is obtained from FIG. 33C2-Co(OH)(CO3)0.5The electrochemical performance is good, the CV curve graph is close to a regular rectangle, and the symmetry is good; the area formed by the cyclic curve increases with the increase of the scanning speed, but the approximate shape of the graph is basically unchanged, and good rate performance is shown.
Step four, Ti3C2-Co(OH)(CO3)0.5Preparing an electrode;
firstly, the foamed nickel is cut into 1 x 2cm2The size of the rectangle is 200mg of active substance, namely Ti obtained in the third step3C2@Co(OH)(CO3)0.5Grinding the nano powder, 2mg of conductive acetylene black and 1mg of polyvinylidene fluoride in an agate mortar for 1-2 h; secondly, sucking 300 mu L of NMP by a liquid transfer gun, grinding uniformly, then evenly dripping the slurry on the cut foam nickel, and drying the dripped foam nickel in a vacuum drying oven for 24 hours at 60 ℃; thirdly, keeping the pressure of the prepared electrode slice at 15MPa for 1min under a tablet press to obtain Ti3C2@Co(OH)(CO3)0.5And an electrode.
Finally, a three-electrode system is adopted, and Ti is used3C2@Co(OH)(CO3)0.5The electrode is used as a working electrode, a platinum sheet is used as a counter electrode, silver and silver chloride are used as reference electrodes, and Ti is tested by using the electrochemical workstation CHI660E in Shanghai Chen Hua under 6M KOH electrolyte3C2@Co(OH)(CO3)0.5The electrochemical performance of the electrode, such as cyclic voltammetry curve, constant current charging and discharging, and alternating current impedance.
Example four
The embodiment comprises the following steps:
step one, ternary Ti3AlC2Preparing ceramic powder;
preparation of ternary layered Ti according to the method of patent ZL201310497696.93AlC2Ceramic powder: first, according to the molar ratio Ti: al: 1.0 part of TiC: 1.2: 2.0 mixing the three raw materials; secondly, placing the three raw materials in a ball milling tank, taking alumina balls as a grinding medium, taking absolute ethyl alcohol as a ball milling auxiliary agent, setting the rotating speed of the ball mill at 900 revolutions per minute, and taking the raw materials as balls according to the mass ratio: material preparation: ethanol ═ 3.0: 1.0: 1.0, performing common ball milling for 1h to obtain uniform powder, and drying the powder in a constant-temperature drying oven at 40 ℃; then, the dried mixed material is placed in a corundum crucible, a vacuum pressureless sintering method is adopted, the temperature is increased to 1350 ℃ at the heating rate of 8 ℃/min, the temperature is kept for 1h, and the mixture is cooled to room temperature along with the furnace to obtain high-purity Ti3AlC2Ceramic powder.
Finally, to Ti3AlC2Carrying out wet high-energy ball milling on the ceramic powder for 3 hours, once every 30 minutes, rotating at the rotating speed of 400r/min, wherein the mass ratio of the steel balls to the ceramic powder is 10:1, and sieving the ground powder to obtain Ti with the particle size of less than 38 mu m3AlC2Ceramic powder.
Step two, two-dimensional layered Ti3C2Preparing a nano material;
preparation of two-dimensional layered Ti according to the method of patent 201410812056.73C2Taking 5g of Ti obtained in the step (I)3AlC2The ceramic powder is slowly immersed in 100mL of 40 wt% hydrofluoric acid solutionAnd magnetically stirring at room temperature for 48h at the rotation speed of 1200r/min until no air bubbles are generated, centrifugally cleaning the corrosion product by using deionized water until the pH value of the supernatant is about 5-6, and centrifuging for 4 times by using absolute ethyl alcohol. Finally, vacuum drying the black precipitate for 24 hours at 40 ℃ to obtain the two-dimensional layered Ti3C2And (3) nano powder.
Step three, Ti3C2-Co(OH)(CO3)0.5Preparing a nano composite material;
first, 145.5mg of Co (NO)3)2·6H2O and Ti obtained in the step (2)3C2Dissolving 200mg of nano powder in ultrapure water, and sequentially adding 100mg of CO (NH) under magnetic stirring2)2Continuously stirring the mixed solution and 200mg of PVP for 2 hours to obtain mixed solution; secondly, transferring the mixed solution with the volume fraction of 75% into a polytetrafluoroethylene lining of a 100ml hydrothermal reaction kettle, heating the assembled hydrothermal reaction kettle to 82 ℃, and preserving the heat for 8 hours; then, the product naturally cooled to room temperature is respectively centrifugally separated and cleaned for 3 times by sequentially using ultrapure water and absolute ethyl alcohol, and is centrifuged for 3-5min at the speed of 4000-; finally, drying the Ti in a vacuum drying oven at 40 ℃ for 24 hours to obtain the required Ti3C2@Co(OH)(CO3)0.5A nanocomposite material. As can be seen from the d-curve of fig. 1, when 2 θ is 36 °, 42 °, 62 ° respectively corresponds to Ti of the (111), (200), (220) crystal planes3C2In addition to the characteristic peaks, the peaks are also Co (OH) (CO) with 2 theta being 18 degrees, 25 degrees and 34 degrees corresponding to PDF standard card numbers of 48-00833)0.5Diffraction peaks of (020), (111), and (221) crystal planes of (A). Shows that Ti is successfully prepared by a hydrothermal method3C2@ precursor Co (OH) (CO)3)0.5A composite material. As can be seen from plot d of FIG. 2, Co (OH) (CO)3)0.5Is uniformly distributed in Ti3C2The interlayer content is high, and no agglomeration occurs.
Step four, Ti3C2-Co(OH)(CO3)0.5Preparing an electrode;
firstly, the foamed nickel is cut into 1 x 2cm2A rectangle with a size of 200mg is sequentially weighed, namely step threeObtained Ti3C2@Co(OH)(CO3)0.5Grinding the nano powder, 2mg of conductive acetylene black and 1mg of polyvinylidene fluoride in an agate mortar for 1-2 h; secondly, sucking 300 mu L of NMP by a liquid transfer gun, grinding uniformly, then evenly dripping the slurry on the cut foam nickel, and drying the dripped foam nickel in a vacuum drying oven for 24 hours at 60 ℃; thirdly, keeping the pressure of the prepared electrode slice at 15MPa for 1min under a tablet press to obtain Ti3C2@Co(OH)(CO3)0.5And an electrode.
Finally, a three-electrode system is adopted, and Ti is used3C2@Co(OH)(CO3)0.5The electrode is used as a working electrode, a platinum sheet is used as a counter electrode, silver and silver chloride are used as reference electrodes, and Ti is tested by using the electrochemical workstation CHI660E in Shanghai Chen Hua under 6M KOH electrolyte3C2@Co(OH)(CO3)0.5The electrochemical performance of the electrode, such as cyclic voltammetry curve, constant current charging and discharging, and alternating current impedance.

Claims (4)

1. Based on Ti3C2-Co(OH)(CO3)0.5The preparation method of the electrode made of the nano composite material is characterized by comprising the following steps:
step one, preparing ternary Ti3AlC2Ceramic powder;
step two, preparing two-dimensional layered Ti3C2A nanomaterial;
step three, Ti3C2-Co(OH)(CO3)0.5Preparing a nano composite material;
first, 145.5-1164mg of Co (NO)3)2·6H2O and the two-dimensional layered Ti obtained in the step (2)3C2Dissolving 200mg of nano powder in ultrapure water, and sequentially adding 100-800mg of CO (NH) under magnetic stirring2)2And 200 and 1600g PVP are continuously stirred for 0.5 to 2 hours to obtain mixed solution; secondly, transferring the mixed solution with the volume fraction of 75% into a polytetrafluoroethylene lining of a 100ml hydrothermal reaction kettle, heating the assembled hydrothermal reaction kettle to 80-85 ℃, and preserving the heat for 6-12 h; then naturally cooling to room temperatureRespectively centrifugally separating and cleaning the materials by ultrapure water and absolute ethyl alcohol for 3 times in sequence, and centrifuging for 3-5min at 4000-; finally, drying in a vacuum drying oven at 40 ℃ for 12-24h to obtain the required Ti3C2@Co(OH)(CO3)0.5A nanocomposite;
step four, Ti3C2-Co(OH)(CO3)0.5Preparing an electrode;
firstly, cutting the foamed nickel into a rectangle with the size of 1 multiplied by 2cm, and sequentially weighing 160-200mg of active substances, namely Ti obtained in the third step3C2@Co(OH)(CO3)0.5Grinding the nano powder, 20-30mg of conductive acetylene black and 1-10mg of polyvinylidene fluoride in an agate mortar for 1-2 h; secondly, sucking 300 mu L of NMP by a liquid transfer gun, grinding uniformly, then evenly dripping the slurry on the cut foam nickel, and drying the dripped foam nickel for 12-24h in a vacuum drying oven at the temperature of 60-80 ℃; thirdly, keeping the pressure of the prepared electrode slice at 15-20Mpa for 1min under a tablet press to obtain Ti3C2@Co(OH)(CO3)0.5And an electrode.
2. A Ti-based alloy according to claim 13C2-Co(OH)(CO3)0.5The preparation method of the electrode of the nano composite material is characterized in that the first step is used for preparing the ternary layered Ti3AlC2The ceramic powder specifically comprises: first, according to the molar ratio Ti: al: 1.0 part of TiC: 1.2: 2.0 mixing the three raw materials; secondly, placing the three raw materials in a ball milling tank, taking alumina balls as a grinding medium, taking absolute ethyl alcohol as a ball milling auxiliary agent, setting the rotating speed of the ball mill at 900 revolutions per minute, and taking the raw materials as balls according to the mass ratio: material preparation: ethanol ═ 3.0: 1.0: 1.0, performing common ball milling for 1h to obtain uniform powder, and drying the powder in a constant-temperature drying oven at 40 ℃; then, the dried mixed material is placed in a corundum crucible, a vacuum pressureless sintering method is adopted, the temperature is increased to 1350 ℃ at the heating rate of 8 ℃/min, the temperature is kept for 1h, and the mixture is cooled to room temperature along with the furnace to obtain high-purity Ti3AlC2Ceramic powder; finally, to Ti3AlC2Carrying out wet high-energy ball milling on the ceramic powder for 3 hours, wherein each 30 minutesOnce in a clock, the rotating speed is 400r/min, the mass ratio of the steel ball to the ceramic powder is 10:1, and the ground powder is sieved to obtain the ternary Ti with the grain diameter of less than 38 mu m3AlC2Ceramic powder.
3. A Ti-based alloy according to claim 13C2-Co(OH)(CO3)0.5The preparation method of the electrode of the nano composite material is characterized in that the two-dimensional layered Ti is prepared in the second step3C2The nano material specifically comprises: taking 5g of Ti obtained in the step (one)3AlC2Slowly immersing the ceramic powder in 100mL of 40 wt% hydrofluoric acid solution, magnetically stirring the ceramic powder at room temperature for 48 hours after bubbling is avoided, rotating at 1200r/min, centrifugally cleaning the corrosion product by deionized water until the pH value of a supernatant is 5-6, centrifuging for 4 times by using absolute ethyl alcohol, and finally vacuum drying black precipitate at 40 ℃ for 24 hours to obtain the two-dimensional layered Ti3C2And (3) nano powder.
4. A Ti-based alloy according to claim 13C2-Co(OH)(CO3)0.5A method for preparing an electrode of a nanocomposite material,
step one, ternary Ti3AlC2Preparing ceramic powder;
first, according to the molar ratio Ti: al: 1.0 part of TiC: 1.2: 2.0 mixing the three raw materials; secondly, placing the three raw materials in a ball milling tank, taking alumina balls as a grinding medium, taking absolute ethyl alcohol as a ball milling auxiliary agent, setting the rotating speed of the ball mill at 900 revolutions per minute, and taking the raw materials as balls according to the mass ratio: material preparation: ethanol ═ 3.0: 1.0: 1.0, performing common ball milling for 1h to obtain uniform powder, and drying the powder in a constant-temperature drying oven at 40 ℃; then, the dried mixed material is placed in a corundum crucible, a vacuum pressureless sintering method is adopted, the temperature is increased to 1350 ℃ at the heating rate of 8 ℃/min, the temperature is kept for 1h, and the mixture is cooled to room temperature along with the furnace to obtain high-purity Ti3AlC2Ceramic powder;
finally, to Ti3AlC2Carrying out wet high-energy ball milling on the ceramic powder for 3 hours, wherein the ball milling time is one minute per 30 minutesSecondly, rotating at the speed of 400r/min, wherein the mass ratio of the steel balls to the ceramic powder is 10:1, and sieving the ground powder to obtain Ti with the particle size of less than 38 mu m3AlC2Ceramic powder;
step two, two-dimensional layered Ti3C2Preparing a nano material;
taking 5g of Ti obtained in the step (one)3AlC2Slowly immersing the ceramic powder in 100mL of 40 wt% hydrofluoric acid solution, magnetically stirring the ceramic powder at room temperature for 48 hours after bubbling is avoided, wherein the rotating speed is 1200r/min, centrifugally cleaning the corrosion product by using deionized water until the pH value of a supernatant is 5-6, and centrifuging for 4 times by using absolute ethyl alcohol; finally, vacuum drying the black precipitate for 24 hours at 40 ℃ to obtain the two-dimensional layered Ti3C2Nano powder;
step three, Ti3C2-Co(OH)(CO3)0.5Preparing a nano composite material;
first, 291.0mg of Co (NO)3)2·6H2O and Ti obtained in the step (2)3C2Dissolving nanometer powder 200mg in ultrapure water, adding CO (NH) 200mg under magnetic stirring2)2Continuously stirring the mixed solution and 400mg of PVP for 2 hours to obtain mixed solution; secondly, transferring the mixed solution with the volume fraction of 75% into a polytetrafluoroethylene lining of a 100ml hydrothermal reaction kettle, heating the assembled hydrothermal reaction kettle to 82 ℃, and preserving the heat for 8 hours; then, the product naturally cooled to room temperature is respectively centrifugally separated and cleaned for 3 times by sequentially using ultrapure water and absolute ethyl alcohol, and is centrifuged for 3-5min at the speed of 4000-; finally, drying the Ti in a vacuum drying oven at 40 ℃ for 24 hours to obtain the required Ti3C2@Co(OH)(CO3)0.5A nanocomposite;
step four, Ti3C2-Co(OH)(CO3)0.5Preparing an electrode;
firstly, cutting the foamed nickel into a rectangle with the size of 1 multiplied by 2cm, and sequentially weighing 200mg of active substances, namely Ti obtained in the third step3C2@Co(OH)(CO3)0.5Grinding the nano powder, 2mg of conductive acetylene black and 1mg of polyvinylidene fluoride in an agate mortar for 1-2 h; secondly, suck with a pipetteUniformly grinding 300 mu L of NMP, uniformly dripping the slurry on the cut foam nickel, and drying the dripped foam nickel in a vacuum drying oven at 60 ℃ for 24 hours; thirdly, keeping the pressure of the prepared electrode slice at 15MPa for 1min under a tablet press to obtain Ti3C2@Co(OH)(CO3)0.5And an electrode.
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