CN114824221A - Titanium dioxide coated CoSe 2 Base nano material and preparation method and application thereof - Google Patents
Titanium dioxide coated CoSe 2 Base nano material and preparation method and application thereof Download PDFInfo
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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Abstract
The invention provides a titanium dioxide coated CoSe 2 A base nano material and a preparation method and application thereof. The preparation method comprises the steps of preparing a Co-Co PBA microcube with a nano size; ultrasonically dispersing Co-Co PBA microcubes in a mixed solution of absolute ethyl alcohol and a concentrated ammonia solution by 0.5-1mLmin ‑1 Dropping organic solution of titanate into the mixed solution at the speed of (1), heating for 5-8h at 70-100 ℃ in an oil bath, standing for 20-24h at room temperature, cleaning the product with a solvent after the reaction is finished, and centrifugally collecting to obtain Co-Co PBA @ TiO 2 (ii) a Mixing Co-Co PBA @ TiO 2 Grinding with selenium powder, selenizing and carbonizing at high temperature under the protection of inert gas to obtain dioxygenTitanium-coated CoSe 2 Base nanomaterial TNC-CoSe 2 . The nano material is used as a negative electrode material of a sodium ion battery, and has ultrahigh multiplying power and cycling stability.
Description
Technical Field
The invention relates to a preparation method of a nano material, in particular to titanium dioxide coated CoSe 2 A preparation method of a base nano material, which belongs toIn the technical field of sodium ion materials.
Background
Sodium Ion Batteries (SIBs) have similar structural features and electrochemical principles to those of Lithium Ion Batteries (LIBs), and have attracted extensive attention from researchers due to the abundance of sodium raw materials and low cost. However, the large radius of Na + and slow diffusion kinetics limit the practical application of sodium ion batteries. The lithium ion battery mainly uses a graphite negative electrode, and the materials have good lithium intercalation characteristics, but for the sodium ion battery, the sodium intercalation efficiency is low, and the specific capacity is only 31mAh g -1 . Accordingly, scientists have been working on developing negative electrode materials with high specific capacity for sodium ion batteries. Wherein, CoSe 2 The method has the advantages of rich reserve, environmental friendliness, small band gap, easy regulation and control of form, high theoretical specific capacity and the like, and is favored by a plurality of topic groups at home and abroad. However, practical application thereof is limited by the disadvantages of poor conductivity, slow reaction kinetics, significant and unstable electrode-electrolyte interface and the like, and even at low rates, the charge-discharge specific capacity may be rapidly attenuated, so that the battery fails.
It is reported that by reasonably constructing the nanostructure, not only the reaction kinetics of the electrode material can be improved, but also the material pulverization caused by the large volume expansion can be relieved. In addition, compounding with a conductive matrix is also a modification method commonly used by researchers. Among them, the carbon layer doped with hetero atoms exhibits excellent conductivity. Particularly, the nitrogen-doped carbon layer can effectively generate defects and improve the conductivity of the material, thereby improving the sodium storage performance of the composite electrode material. The Prussian Blue Analogue (PBA) is a nitrogen-rich carbon-based material, and can form a conductive network after heat treatment, so that the conductivity of the material can be obviously improved, and the electrochemical performance of the composite material can be effectively improved. On the other hand, TiO is known 2 Is a promising anode material and has a plurality of characteristics which are worthy of study: low cost, structural robustness and negligible volume change due to its layered crystal structure. Compared with the traditional conductive coating, the conductive coating also has redox activity and can be used on the premise of not losing capacityIn the following, the stability of the structure and the interface is further enhanced.
Therefore, it is necessary to use TiO 2 As a coating to mitigate volume changes of TMDs and provide a reasonable path for charge transfer.
Disclosure of Invention
The invention aims to provide an optimized CoSe 2 Titanium dioxide coated CoSe prepared based on Prussian blue analogue template and provided by performance of base material in sodium ion battery 2 Base nanomaterial (TNC-CoSe) 2 ) The method of (1).
In order to achieve the above technical objects, the present invention first provides a titanium dioxide coated CoSe 2 The preparation method of the base nanometer material comprises the following steps:
preparing a Co-Co PBA microcube with a nano size; adding cobalt acetate, potassium hexacyanocarboxylate and sodium dodecyl sulfate into water, performing ultrasonic dispersion uniformly, stirring by intense magnetic force for 1-3h, standing for 20-24h at 25 ℃, centrifugally collecting precipitates by using absolute ethyl alcohol as a solvent, and drying for 8-12 h at 60-80 ℃ to prepare a Co-Co PBA microcube with a nano size; wherein the mixing ratio of the cobalt acetate, the potassium hexacyanocarboxylate and the sodium dodecyl sulfate is 1: (1-2): (90-120);
ultrasonically dispersing Co-Co PBA microcubes in a mixed solution of absolute ethyl alcohol and a concentrated ammonia solution for 0.5-1mL min -1 Dropping organic solution of titanate into the mixed solution at the speed, heating for 5-8h at 70-100 ℃ in an oil bath, standing for 20-24h at room temperature, cleaning the product with solvent after the reaction is finished, and centrifugally collecting to obtain Co-Co PBA @ TiO 2 (ii) a (ii) a Wherein, the ratio of the Co-Co PBA microcubes to the absolute ethyl alcohol is (0.1-0.3) g: (60-100) mL;
mixing Co-Co PBA @ TiO 2 Evenly grinding the mixture and selenium powder, and carrying out high-temperature selenization and carbonization under the protection of inert gas to obtain the titanium dioxide coated CoSe 2 Based on nano-materials (black powder prepared with TiO on the outside) 2 Nitrogen doped carbon CoSe protected by coating 2 Composite material (TNC-CoSe) 2 ) Co-Co PBA @ TiO) in which 2 And the selenium powder in a mixing mass ratio of 1: 3-6.
Prussian blue analogue (Co) used in the invention 3 [Co(CN) 6 ] 2 Co-Co PBA) as precursor, coating a layer of TiO by sol-gel method 2 Coating, and synthesizing with TiO outside by high-temperature heat treatment 2 Nitrogen doped carbon CoSe protected by coating 2 Composite material (TNC-CoSe) 2 ) The material keeps the original cubic shape, and the nitrogen-doped carbon skeleton can promote interface electron transmission, so that the promotion of reaction kinetics is promoted; second, TiO 2 The protective layer effectively relieves CoSe due to its excellent structural stability 2 The volume of the material expands in the circulating process, and the material can be prevented from falling off and powdering; finally, this heterostructure facilitates pseudocapacitive charge storage, resulting in superior cycling stability performance at ultra-high rates.
In one embodiment of the present invention, the titanium ester used is one selected from tetrabutyl titanate, tetraethyl titanate, tetrapropyl titanate.
In one embodiment of the present invention, the organic solution is selected from one of acetic acid, isopropanol, n-butanol, and acetylacetone.
In one embodiment of the present invention, the amount of the titanate added to the organic solution of titanate is 100. mu.L-300. mu.L per 60-100mL of the organic solution.
In one embodiment of the invention, the concentration of the concentrated ammonia solution in the mixed solution of the absolute ethyl alcohol and the concentrated ammonia solution is 20-28 wt%.
In one embodiment of the present invention, the inert gas is selected from one of argon, nitrogen, argon-hydrogen mixture; wherein the volume ratio of argon to hydrogen in the argon-hydrogen mixed gas is 95% to 5%.
In one embodiment of the present invention, the flow rate of the inert gas is 50 to 150mL min -1 。
In a specific embodiment of the invention, the temperature of high-temperature selenization and carbonization is 300-450 ℃, and the holding time is 3-6 h.
The invention also provides titanium dioxide coated CoSe 2 Based on a nanomaterial, the titanium dioxide-coated CoSe 2 CoSe coated with the titanium dioxide of the invention when based on nanomaterials 2 The base nano material is prepared by the preparation method.
The above-mentioned titanium dioxide-coated CoSe of the present invention 2 Application of base nano material, the titanium dioxide coated CoSe 2 The base nano material is used as a negative electrode material of a sodium ion battery.
In one embodiment of the present invention, TNC-CoSe is added 2 The particles are coated on the copper foil to prepare the negative electrode of the sodium-ion battery. Mixing TNC-CoSe 2 The particles, the conductive agent (Super P) and the binder (sodium carboxymethyl cellulose (CMC)) are dispersed in the aqueous solvent according to the mass ratio of 8:1:1, and then the particles, the conductive agent and the binder are uniformly coated on the copper foil and are dried to prepare the circular electrode slice with the diameter of 12 mm.
In the present invention, CoSe 2 The electrochemical performance test of the cathode material adopts a sodium ion battery system consisting of double electrodes. Wherein, CoSe 2 The base material was used as the working electrode and the high purity sodium sheet was used as the counter electrode. In a glove box (H2O) filled with high-purity argon (99.999 percent)<0.01ppm，O2<0.01ppm) was assembled into a 2032-type coin cell. In a button cell, glass fiber (Whatman, GF/D) was used as a separator, 1M NaClO4 was dissolved in Ethylene Carbonate (EC)/dimethyl carbonate (DMC) (1:1v/v) and 5 wt% fluoroethylene carbonate (FEC) was added as an electrolyte. The charge and discharge experiments of the sodium ion battery were performed on the novice battery test system.
Titanium dioxide coated CoSe of the invention 2 The preparation method of the base nano material is based on a self-sacrifice template method taking Prussian blue analogue as precursor, and can synthesize the titanium dioxide coated CoSe 2 And (3) a base nanomaterial. Co-Co PBA microcubes prepared by coprecipitation method and Co-Co PBA @ TiO prepared by sol-gel method 2 And finally, the composite material is synthesized by a solid phase method, the preparation method is simple and easy to operate, the energy consumption is relatively low, and the composite material is carried out in a closed container and has little pollution.
TNC-CoSe prepared by using method provided by the invention 2 When the material is used for a negative electrode material of a sodium-ion battery, the advantages are as follows: the product retains Prussian blue analogueCharacteristic cubic morphology, small size CoSe 2 The microcubes and nitrogen-doped carbon skeleton can promote interfacial electron transport, thereby generating rapid reaction kinetics; and externally coated TiO 2 The coating can be adapted to CoSe as a buffer layer 2 The volume effect of (a); in addition, the material also has a larger specific surface area, so that the contact resistance of the electrode material and the electrolyte is small, and the cycle performance and the rate capability of the battery are improved.
Drawings
FIG. 1 is a titanium dioxide coated CoSe prepared in example 2 2 Base nanomaterial (TNC-CoSe) 2 -200) SEM images;
FIG. 2 is a titanium dioxide coated CoSe prepared in example 2 2 Base nanomaterial (TNC-CoSe) 2 -200) TEM images;
FIG. 3 shows CoSe prepared in Experimental example 1 and example 2 without coating with titanium dioxide 2 Base nanomaterial (NC-CoSe) 2 -200) and titanium dioxide coated CoSe 2 Base nanomaterial (TNC-CoSe) 2 -200) BET plot;
FIG. 4 shows CoSe prepared in Experimental example 1 and example 2 without coating with titanium dioxide 2 Base nanomaterial (NC-CoSe) 2 -200) and titanium dioxide coated CoSe 2 Base nanomaterial (TNC-CoSe) 2 -200) charge-discharge cycle performance diagram;
FIG. 5 shows CoSe prepared in Experimental example 1 and example 2 without coating with titanium dioxide 2 Base nanomaterial (NC-CoSe) 2 -200) and titanium dioxide coated CoSe 2 Base nanomaterial (TNC-CoSe) 2 200) SEM picture.
Detailed Description
The invention is based on the preparation of titanium dioxide coated CoSe by a Prussian blue analogue template 2 The preparation method of the base nanometer material also comprises the following steps:
(a) weighing cobalt acetate, potassium hexacyanocoarboxylate and sodium dodecyl sulfate, adding into a certain amount of deionized water, ultrasonically dispersing uniformly, stirring by intense magnetic force for about 1h, and standing for 24h at 25 ℃. The precipitate was collected by centrifugation using absolute ethanol as a solvent and dried at 60 ℃ for 12 hours.
(b) Uniformly and ultrasonically dispersing the Co-Co PBA microcubes synthesized in the step (a) into a mixed solution of absolute ethyl alcohol and concentrated ammonia solution (28 wt%), and then using a pipette gun for 1mL min -1 To the mixed solution was added dropwise an organic solution of a titanium ester. After heating in an oil bath for 5 hours, standing for 24 hours at room temperature. After the reaction is finished, cleaning the product by using a solvent and centrifugally collecting to obtain Co-Co PBA @ TiO 2 And (3) obtaining the product.
(c) Firstly, the Co-Co PBA @ TiO synthesized in the step (b) is added 2 And selenium powder are uniformly ground and dispersed in a ceramic boat. Subsequently, the mixture is subjected to high-temperature heat treatment under the protection of inert gas. The prepared black powder is provided with TiO outside 2 Nitrogen doped carbon CoSe protected by coating 2 Composite material (TNC-CoSe) 2 )。
The obtained product has TiO 2 Nitrogen doped carbon CoSe protected by coating 2 Composite material (TNC-CoSe) 2 ) For assembling button cells, in particular: mixing TNC-CoSe 2 Dispersing particles, conductive agent (Super P) and binder (sodium carboxymethylcellulose (CMC)) in water solvent at a mass ratio of 8:1:1, uniformly coating on copper foil, drying to obtain circular electrode sheet with diameter of 12mm, using the electrode sheet as working electrode, using high purity sodium sheet as counter electrode, and placing in glove box (H) filled with high purity argon (99.999%) ( 2 O<0.01ppm，O 2 <0.01ppm) was assembled into a 2032 type coin cell. In button cells, glass fiber (Whatman, GF/D) was used as separator, 1M NaClO 4 Dissolved in Ethylene Carbonate (EC)/dimethyl carbonate (DMC) (1:1v/v) and 5 wt% fluoroethylene carbonate (FEC) was added as an electrolyte. The charge and discharge experiments of the sodium ion battery were performed on the novice battery test system.
Example 1
The present example provides a TNC-CoSe 2 -100 a method for preparing a composite electrode material, comprising the steps of:
(a) 0.2g of cobalt acetate, 0.265g of potassium hexacyanocarboxylate and 5.4g of sodium dodecyl sulfate are added into 400mL of deionized water, uniformly dispersed by ultrasonic waves, stirred by intense magnetic force for about 1 hour and kept stand for 24 hours at 25 ℃. The precipitate was collected by centrifugation using absolute ethanol as a solvent and dried at 60 ℃ for 12 hours.
(b) Uniformly and ultrasonically dispersing 0.2g of Co-Co PBA synthesized in the step (a) in a mixed solution of 60mL of absolute ethyl alcohol and 0.15mL of concentrated ammonia solution (28wt percent) for 30 minutes, and then dispersing for 1mL min -1 To the mixed solution, 100. mu.L of tetrabutyl titanate (TBOT) was added dropwise. Heating in an oil bath at 80 ℃ for 5h, and standing at 25 ℃ for 24 h. Centrifuging for four times by using absolute ethyl alcohol as a solvent, and drying in an oven at 70 ℃ for 8 h.
(c) 0.2g of Co-Co PBA @ TiO synthesized in step (b) 2 And 0.8g of selenium powder were uniformly ground and dispersed in a ceramic boat. Subsequently, the mixture was placed in Ar/H 2 (volume ratio 95:5) at 350 ℃ for 4 hours. The black powder prepared was TNC-CoSe 2 。
Reacting TNC-CoSe 2 Dispersing 100 particles, conductive agent (Super P) and binder (sodium carboxymethylcellulose (CMC)) in water solvent at a mass ratio of 8:1:1, uniformly coating on copper foil, drying to obtain circular electrode sheet with diameter of 12mm, and using the electrode sheet as working electrode, high-purity sodium sheet as counter electrode, and placing in glove box (H) filled with high-purity argon (99.999%)) 2 O<0.01ppm，O 2 <0.01ppm) was assembled into a 2032-type coin cell. In button cells, glass fiber (Whatman, GF/D) was used as separator, 1M NaClO 4 Dissolved in Ethylene Carbonate (EC)/dimethyl carbonate (DMC) (1:1v/v) and 5 wt% fluoroethylene carbonate (FEC) was added as an electrolyte. The charge and discharge experiments of the sodium ion battery were performed on the novice battery test system.
Example 2
The present example provides a TNC-CoSe 2 -200 a method for preparing a composite electrode material, comprising the steps of:
(a) 0.2g of cobalt acetate, 0.265g of potassium hexacyanocarboxylate and 5.4g of sodium dodecyl sulfate are added into 400mL of deionized water, uniformly dispersed by ultrasonic waves, stirred by intense magnetic force for about 1 hour and kept stand for 24 hours at 25 ℃. The precipitate was collected by centrifugation using absolute ethanol as a solvent and dried at 60 ℃ for 12 hours.
(b) Uniformly and ultrasonically dispersing 0.2g of Co-Co PBA synthesized in the step (a) in a mixed solution of 60mL of absolute ethyl alcohol and 0.15mL of concentrated ammonia solution (28wt percent) for 30 minutes, and then dispersing for 1mL min -1 To the mixed solution was added dropwise 200. mu.L of tetrabutyl titanate (TBOT). Heating in oil bath at 80 deg.C for 5 hr, and standing at 25 deg.C for 24 hr. The mixture is centrifuged for four times by using absolute ethyl alcohol as a solvent and dried in an oven at 70 ℃ for 8 hours.
(c) 0.2g of Co-Co PBA @ TiO synthesized in step (b) 2 And 0.8g of selenium powder were uniformly ground and dispersed in a ceramic boat. Subsequently, the mixture was placed in Ar/H 2 (volume ratio 95:5) at 350 ℃ for 4 hours. The black powder prepared was TNC-CoSe 2 。
Mixing TNC-CoSe 2 Dispersing-200 particles, conductive agent (Super P) and binder (sodium carboxymethylcellulose (CMC)) in water solvent at a mass ratio of 8:1:1, uniformly coating on copper foil, drying to obtain circular electrode sheet with diameter of 12mm, and using the electrode sheet as working electrode, high-purity sodium sheet as counter electrode, and loading in glove box (H) filled with high-purity argon (99.999%)) 2 O<0.01ppm，O 2 <0.01ppm) was assembled into a 2032-type coin cell. In button cells, glass fiber (Whatman, GF/D) was used as separator, 1M NaClO 4 Dissolved in Ethylene Carbonate (EC)/dimethyl carbonate (DMC) (1:1v/v) and 5 wt% fluoroethylene carbonate (FEC) was added as an electrolyte. The charge and discharge experiments of the sodium ion battery were performed on the novice battery test system. As shown in SEM of FIG. 1, the surface of the material became rougher after coating titanium dioxide by the sol-gel method, demonstrating that TiO 2 Coating with CoSe 2 A surface. Furthermore, the concave surface of the cubic particles is due to the pyrolysis and selenization process of the pre-precursor, resulting in local shrinkage. As shown in FIG. 2, TNC-CoSe was observed under low power transmission electron microscope 2 Indicating cubic CoSe 2 The surface is coated with a layer of uniform and continuous TiO 2 . Apparently, TiO 2 Reserves NC-CoSe 2 And a cubic NC-CoSe is successfully established 2 Is a core, a layer of TiO 2 Is a core-shell structure of the shell. N in FIG. 3 2 Adsorption and desorptionIsotherm display of NC-CoSe 2 And TNC-CoSe 2 The Brunauer-Emmett-Teller (BET) surface areas of 14.18 and 23.52m, respectively 2 g -1 . The test shows that the increase in BET is Na + Provides additional intercalation sites and enhances pseudocapacitance contribution, thereby improving its electrochemical performance. As shown in FIG. 4, the result of the charge and discharge test shows that TNC-CoSe 2 The specific capacity of the composite electrode material is stabilized at 511.2mAh g after 200 times of circulation -1 The capacity retention was 81.95% from cycle 4, indicating that this carefully designed material did not experience a large volume effect during repeated charge and discharge cycles. Comparison found, NC-CoSe 2 The capacity loss is relatively fast when the composite electrode material is cycled, and the battery completely fails after 200 cycles of cycling. TNC-CoSe according to the SEM image after both cycles shown in FIG. 5 2 The sample still maintains a relatively complete cubic structure after the composite electrode material is cycled, and NC-CoSe 2 The cubic structure of the electrode material has collapsed through charge and discharge cycles and some of the nanoparticles have agglomerated together.
Example 3
The present example provides a TNC-CoSe 2 -300 a method for preparing a composite electrode material, comprising the steps of:
(a) 0.2g of cobalt acetate, 0.265g of potassium hexacyanocarboxylate and 5.4g of sodium dodecyl sulfate are added into 400mL of deionized water, uniformly dispersed by ultrasonic waves, stirred by intense magnetic force for about 1 hour and kept stand for 24 hours at 25 ℃. The precipitate was collected by centrifugation using absolute ethanol as a solvent and dried at 60 ℃ for 12 hours.
(b) Uniformly and ultrasonically dispersing 0.2g of Co-Co PBA synthesized in the step (a) in a mixed solution of 60mL of absolute ethyl alcohol and 0.15mL of concentrated ammonia solution (28wt percent) for 30 minutes, and then dispersing for 1mL min -1 300. mu.L of tetrabutyl titanate (TBOT) was added dropwise to the mixed solution. Heating in an oil bath at 80 ℃ for 5h, and standing at 25 ℃ for 24 h. The mixture is centrifuged for four times by using absolute ethyl alcohol as a solvent and dried in an oven at 70 ℃ for 8 hours.
(c) 0.2g of Co-Co PBA @ TiO synthesized in step (b) 2 And 0.8g of selenium powder were uniformly ground and dispersed in a ceramic boat. Subsequently, the mixture was placed in Ar/H 2 (volume ratio 95:5) at 350 ℃ in an atmosphereHeat and incubate for 4 hours. The black powder prepared was TNC-CoSe 2 。
Mixing TNC-CoSe 2 300 particles, a conductive agent (Super P) and a binder (sodium carboxymethyl cellulose (CMC)) are dispersed in an aqueous solvent according to a mass ratio of 8:1:1, then the mixture is uniformly coated on a copper foil, and after drying, a circular electrode plate with the diameter of 12mm is prepared and is used as a working electrode, a high-purity sodium plate is used as a counter electrode, and the electrode plate is placed in a glove box (H) filled with high-purity argon (99.999 percent) 2 O<0.01ppm，O 2 <0.01ppm) was assembled into a 2032-type coin cell. In button cells, glass fiber (Whatman, GF/D) was used as separator, 1M NaClO 4 Dissolved in Ethylene Carbonate (EC)/dimethyl carbonate (DMC) (1:1v/v) and 5 wt% fluoroethylene carbonate (FEC) was added as an electrolyte. The charge and discharge experiments of the sodium ion battery were performed on the novice battery test system.
Example 4
The present example provides a TNC-CoSe 2 A method for preparing a composite electrode material at-300 ℃, which comprises the following steps:
(a) 0.2g of cobalt acetate, 0.265g of potassium hexacyanocarboxylate and 5.4g of sodium dodecyl sulfate are added into 400mL of deionized water, uniformly dispersed by ultrasonic waves, stirred by intense magnetic force for about 1 hour and kept stand for 24 hours at 25 ℃. The precipitate was collected by centrifugation using absolute ethanol as a solvent and dried at 60 ℃ for 12 hours.
(b) Uniformly and ultrasonically dispersing 0.2g of Co-Co PBA synthesized in the step (a) in a mixed solution of 60mL of absolute ethyl alcohol and 0.15mL of concentrated ammonia solution (28wt percent) for 30 minutes, and then dispersing for 1mL min -1 To the mixed solution was added dropwise 200. mu.L of tetrabutyltitanate (TBOT). Heating in an oil bath at 80 ℃ for 5h, and standing at 25 ℃ for 24 h. The mixture is centrifuged for four times by using absolute ethyl alcohol as a solvent and dried in an oven at 70 ℃ for 8 hours.
(c) 0.2g of Co-Co PBA @ TiO synthesized in step (b) 2 And 0.8g of selenium powder were uniformly ground and dispersed in a ceramic boat. Subsequently, the mixture was placed in Ar/H 2 (volume ratio 95:5) at 300 ℃ for 4 hours. The black powder prepared was TNC-CoSe 2 。
Mixing TNC-CoSe 2 Dispersing particles at-300 ℃, a conductive agent (Super P) and a binder (sodium carboxymethyl cellulose (CMC)) in a water solvent according to a mass ratio of 8:1:1, then uniformly coating the mixture on a copper foil, drying the mixture to prepare a circular electrode plate with the diameter of 12mm, using the circular electrode plate as a working electrode and a high-purity sodium plate as a counter electrode, and placing the circular electrode plate in a glove box (H) filled with high-purity argon (99.999 percent) 2 O<0.01ppm，O 2 <0.01ppm) was assembled into a 2032-type coin cell. In a button cell, glass fiber (Whatman, GF/D) was used as separator, 1M NaClO 4 Dissolved in Ethylene Carbonate (EC)/dimethyl carbonate (DMC) (1:1v/v) and 5 wt% fluoroethylene carbonate (FEC) was added as an electrolyte. The charge and discharge experiments of the sodium ion battery were performed on a nova battery test system.
Example 5
The present embodiment provides a TNC-CoSe 2 A method for preparing a composite electrode material at-400 ℃, comprising the following steps:
(a) 0.2g of cobalt acetate, 0.265g of potassium hexacyanocarboxylate and 5.4g of sodium dodecyl sulfate are added into 400mL of deionized water, uniformly dispersed by ultrasonic waves, stirred by intense magnetic force for about 1 hour and kept stand for 24 hours at 25 ℃. The precipitate was collected by centrifugation using absolute ethanol as a solvent and dried at 60 ℃ for 12 hours.
(b) Uniformly and ultrasonically dispersing 0.2g of Co-Co PBA synthesized in the step (a) in a mixed solution of 60mL of absolute ethyl alcohol and 0.15mL of concentrated ammonia solution (28wt percent) for 30 minutes, and then dispersing for 1mL min -1 To the mixed solution was added dropwise 200. mu.L of tetrabutyltitanate (TBOT). Heating in an oil bath at 80 ℃ for 5h, and standing at 25 ℃ for 24 h. The mixture is centrifuged for four times by using absolute ethyl alcohol as a solvent and dried in an oven at 70 ℃ for 8 hours.
(c) 0.2g of Co-Co PBA @ TiO synthesized in step (b) 2 And 0.8g of selenium powder were uniformly ground and dispersed in a ceramic boat. Subsequently, the mixture was placed in Ar/H 2 (volume ratio 95:5) at 400 ℃ for 4 hours. The black powder prepared was TNC-CoSe 2 。
Mixing TNC-CoSe 2 Dispersing particles at 400 ℃ below zero, a conductive agent (Super P) and a binder (sodium carboxymethyl cellulose (CMC)) in an aqueous solvent according to a mass ratio of 8:1:1,then uniformly coating on copper foil, drying to obtain circular electrode plate with diameter of 12mm, using it as working electrode, using high-purity sodium plate as counter electrode, placing in glove box (H) filled with high-purity argon (99.999%) 2 O<0.01ppm，O 2 <0.01ppm) was assembled into a 2032-type coin cell. In button cells, glass fiber (Whatman, GF/D) was used as separator, 1M NaClO 4 Dissolved in Ethylene Carbonate (EC)/dimethyl carbonate (DMC) (1:1v/v) and 5 wt% fluoroethylene carbonate (FEC) was added as an electrolyte. The charge and discharge experiments of the sodium ion battery were performed on the novice battery test system.
Example 6
The present example provides a TNC-CoSe 2 A preparation method of a composite electrode material at 450 ℃, which comprises the following steps:
(a) 0.2g of cobalt acetate, 0.265g of potassium hexacyanocarboxylate and 5.4g of sodium dodecyl sulfate are added into 400mL of deionized water, uniformly dispersed by ultrasonic waves, stirred by intense magnetic force for about 1 hour and kept stand for 24 hours at 25 ℃. The precipitate was collected by centrifugation using absolute ethanol as a solvent and dried at 60 ℃ for 12 hours.
(b) Uniformly and ultrasonically dispersing 0.2g of Co-Co PBA synthesized in the step (a) in a mixed solution of 60mL of absolute ethyl alcohol and 0.15mL of concentrated ammonia solution (28wt percent) for 30 minutes, and then dispersing for 1mL min -1 To the mixed solution was added dropwise 200. mu.L of tetrabutyltitanate (TBOT). Heating in an oil bath at 80 ℃ for 5h, and standing at 25 ℃ for 24 h. Centrifuging for four times by using absolute ethyl alcohol as a solvent, and drying in an oven at 70 ℃ for 8 h.
(c) 0.2g of Co-Co PBA @ TiO synthesized in step (b) 2 And 0.8g of selenium powder were uniformly ground and dispersed in a ceramic boat. Subsequently, the mixture was placed in Ar/H 2 (volume ratio 95:5) at 450 ℃ for 4 hours. The black powder prepared was TNC-CoSe 2 。
Mixing TNC-CoSe 2 Dispersing particles at 450 ℃, a conductive agent (Super P) and a binder (sodium carboxymethyl cellulose (CMC)) in a water solvent according to a mass ratio of 8:1:1, then uniformly coating the mixture on a copper foil, drying the mixture to prepare a circular electrode slice with the diameter of 12mm, and using the circular electrode slice as a working electrode, and using a high-purity sodium slice as a counter electrodeElectrode in a glove box (H) filled with high purity argon (99.999%) 2 O<0.01ppm，O 2 <0.01ppm) was assembled into a 2032-type coin cell. In a button cell, glass fiber (Whatman, GF/D) was used as separator, 1M NaClO 4 Dissolved in Ethylene Carbonate (EC)/dimethyl carbonate (DMC) (1:1v/v) and 5 wt% fluoroethylene carbonate (FEC) was added as an electrolyte. The charge and discharge experiments of the sodium ion battery were performed on the novice battery test system.
Comparative example 1
(a) 0.2g of cobalt acetate, 0.265g of potassium hexacyanocarboxylate and 5.4g of sodium dodecyl sulfate are added into 400mL of deionized water, uniformly dispersed by ultrasonic waves, stirred by intense magnetic force for about 1 hour and kept stand for 24 hours at 25 ℃. The precipitate was collected by centrifugation using absolute ethanol as a solvent and dried at 60 ℃ for 12 hours.
(b) 0.2g of Co-Co PBA synthesized in step (a) and 0.8g of selenium powder were uniformly ground and dispersed in a ceramic boat. Subsequently, the mixture was brought to Ar/H 2 (volume ratio 95:5) at 350 ℃ for 4 hours. The black powder prepared was NC-CoSe 2 。
Mixing NC-CoSe 2 Dispersing particles, conductive agent (Super P) and binder (sodium carboxymethylcellulose (CMC)) in water solvent at a mass ratio of 8:1:1, uniformly coating on copper foil, drying to obtain circular electrode plate with diameter of 12mm, using the electrode plate as working electrode, using high-purity sodium plate as counter electrode, and placing in glove box (H) filled with high-purity argon (99.999%) ( 2 O<0.01ppm，O 2 <0.01ppm) was assembled into a 2032 type coin cell. In button cells, glass fiber (Whatman, GF/D) was used as separator, 1M NaClO 4 Dissolved in Ethylene Carbonate (EC)/dimethyl carbonate (DMC) (1:1v/v) and 5 wt% fluoroethylene carbonate (FEC) was added as an electrolyte. The charge and discharge experiments of the sodium ion battery were performed on the novice battery test system.
The batteries of the above examples and comparative examples were subjected to cycle tests, and the results are shown in table 1.
TABLE 1
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (10)
1. Titanium dioxide coated CoSe 2 The preparation method of the base nanometer material comprises the following steps:
adding cobalt acetate, potassium hexacyanocarboxylate and sodium dodecyl sulfate into water, performing ultrasonic dispersion uniformly, stirring by intense magnetic force for 1-3h, standing for 20-24h at 25 ℃, centrifugally collecting precipitates by using absolute ethyl alcohol as a solvent, and drying for 8-12 h at 60-80 ℃ to prepare a Co-Co PBA microcube with a nano size; wherein the mixing mass ratio of the cobalt acetate, the potassium hexacyanocarboxylate and the sodium dodecyl sulfate is 1: (1-2): (25-30);
ultrasonically dispersing the Co-Co PBA microcubes in a mixed solution of absolute ethyl alcohol and a concentrated ammonia solution for 0.5-1mL min -1 Dropping organic solution of titanate into the mixed solution at the speed, heating for 5-8h at 70-100 ℃ in an oil bath, standing for 20-24h at room temperature, cleaning the product with solvent after the reaction is finished, and centrifugally collecting to obtain Co-Co PBA @ TiO 2 (ii) a Wherein, the ratio of the Co-Co PBA microcubes to the absolute ethyl alcohol is (0.1-0.3) g: (60-100) mL;
mixing the Co-Co PBA @ TiO 2 Uniformly grinding the mixture and selenium powder, and carrying out high-temperature selenization and carbonization under the protection of inert gas to obtain titanium dioxide coated CoSe 2 Base nanomaterial TNC-CoSe 2 (ii) a Wherein, Co-Co PBA @ TiO 2 And the selenium powder in a mixing mass ratio of 1: 3-6.
2. The preparation method according to claim 1, wherein the titanium ester is one selected from tetrabutyl titanate, tetraethyl titanate, and tetrapropyl titanate.
3. The preparation method according to claim 1, wherein the organic solution is one selected from acetic acid, isopropyl alcohol, n-butanol, and acetylacetone.
4. The method according to claim 1, wherein the amount of the titanium ester added to the organic solution of titanium ester is 100 to 300. mu.L per 60 to 100mL of the organic solution.
5. The production method according to claim 1, wherein the concentration of the concentrated ammonia solution in the mixed solution of the anhydrous ethanol and the concentrated ammonia solution is 20 to 28 wt%.
6. The production method according to claim 1, wherein the inert gas is selected from one of argon, nitrogen, and argon-hydrogen mixture gas;
preferably, the volume ratio of the argon to the hydrogen in the argon-hydrogen mixed gas is 95% to 5%.
7. The production method according to claim 1 or 6, wherein the flow rate of the inert gas is 50 to 150mL min -1 。
8. The preparation method according to claim 1, wherein the temperature of the high-temperature selenization and carbonization is 300-450 ℃, and the holding time is 3-6 h.
9. Titanium dioxide coated CoSe 2 Based on nanomaterials of titanium dioxide coated CoSe 2 CoSe coated with the titanium dioxide according to any one of claims 1 to 8 when based on nanomaterials 2 The base nano material is prepared by the preparation method.
10. The titanium dioxide-coated CoSe of claim 9 2 Application of base nano material, the titanium dioxide coated CoSe 2 The base nano material is used as a negative electrode material of a sodium ion battery.
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