CN113054187A - V-shaped groove2Preparation method of C-MXene/cobalt-nickel double metal hydroxide composite material - Google Patents
V-shaped groove2Preparation method of C-MXene/cobalt-nickel double metal hydroxide composite material Download PDFInfo
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Abstract
A V of the invention2A preparation method of a C-MXene/cobalt-nickel double metal hydroxide composite material belongs to the technical field of electrochemical energy storage. The preparation process comprises the following steps: v is prepared by specific acid etching2After C-MXene nano material, with V2C-MXene is taken as a substrate, and the one-step hydrothermal method is used for realizing the purpose that the cobalt-nickel metal ions are in V2In-situ growth of C-MXene surface to obtain a film with V2V with C-MXene and cobalt-nickel double metal hydroxide alternately stacked structure2C-MXene/cobalt nickel double metal hydroxide composite material. The composite material has the advantages of excellent conductivity and structural stability of MXene material, higher specific surface area and lithium storage capacity of the double metal hydroxide, good electrochemical performance and specific surface area of 50.25-70.00m2·g‑1The first discharge specific capacity can reach 500 mAh.g‑1The above.
Description
The technical field is as follows:
the invention belongs to the technical field of electrochemical energy storage, and particularly relates to a V2A preparation method of a C-MXene/cobalt-nickel double metal hydroxide composite material.
Background art:
in recent years, with the rapid development of society, the demand of people on energy in various fields is increased sharply, and traditional energy sources such as coal, petroleum and natural gas are far from meeting the production and living demands of people. In addition, environmental problems caused by the increasing depletion of traditional energy sources are becoming important problems for human survival and development. The lithium ion battery has a very wide application prospect due to the advantages of light weight, environmental friendliness, high energy density, good cycle stability and the like, and is widely applied to various fields such as communication, new energy vehicles, military industry and the like.
The selection of the negative electrode material is a key factor for determining the electrochemical performance of the lithium ion battery. Transition metal carbide and nitride (MXene) materials are novel nano materials with two-dimensional layered structures, are similar to graphene in electrochemical performance, have extremely high volume capacitance and reversibility, and have a plurality of advantages of good mechanical strength, conductivity, hydrophilicity, chemical stability and the like due to special element compositions and surface functional groups, so the transition metal carbide and nitride (MXene) materials have good application prospects in the field of lithium ion battery cathode materials. However, MXene materials have the defects of low theoretical capacity and the like.
Cobalt-nickel double metal hydroxide material (CoNi-LDH) has higher electrochemical activity due to the synergistic effect of double metals, thereby showing high theoretical specific capacitance. In addition, the advantages of low cost, controllable interlayer structure and the like of the lithium ion battery lead the lithium ion battery to have good application prospect in the aspect of lithium ion battery cathode materials. However, layered double hydroxide materials (LDHs) themselves have problems of poor conductivity, poor structural stability, and the like. Therefore, LDHs is introduced into an MXene interlayer structure to form an MXene/cobalt-nickel double metal hydroxide composite structure, the composite structure is used as a lithium ion battery cathode material, the conductivity and the structural stability are good, the lithium ion storage capacity is high, and the electrochemical performance of the cathode material can be comprehensively improved.
The invention content is as follows:
the invention aims to overcome the defects in the prior art and provide a V2A preparation method of a C-MXene/cobalt-nickel bimetal hydroxide composite material comprises the steps of selecting a nano material with high theoretical capacity, namely cobalt-nickel bimetal hydroxide, and enabling the cobalt-nickel bimetal hydroxide to be in a V state through electrostatic adsorption2C-MXene surface in-situ growth to form a V2C-MXene/cobalt nickel double metal hydroxide composite material. The method utilizes two self structural characteristics of MXene and LDHs to form a structure that the MXene and the LDHs are stacked mutually. The electrode material has the advantages of both and shows good electrochemical performance.
In order to achieve the purpose, the invention adopts the following technical scheme:
v-shaped groove2The preparation method of the C-MXene/cobalt-nickel double metal hydroxide composite material comprises the following steps:
the method comprises the following steps: preparation of layer V2C-MXene nano material
(1) According to volume ratio, hydrochloric acid solution: sodium fluoride solution ═ (1-3): 1, adding sodium fluoride solution into hydrochloric acid solution, stirring to obtain uniform hydrochloric acid and sodium fluoride mixed solution, and then slowly adding V2Continuously stirring the AlC solution to obtain a uniformly dispersed black mixed solution, wherein the concentration of the sodium fluoride solution is 3-6mol/L, the concentration of the aluminum vanadium carbide solution is 2.5-6mol/L, the mass fraction of the hydrochloric acid solution is 32-38 wt%, and V is the volume ratio of V to V2AlC solution: (sodium fluoride solution + hydrochloric acid solution) ═ 1: (15-25);
(2) transferring the mixed solution into a high-pressure reaction kettle, transferring the high-pressure reaction kettle into a thermostat for hydrothermal reaction, wherein the hydrothermal reaction time is 60-90h, the reaction temperature is 80-120 ℃, and a two-dimensional layered structure compound V is prepared2C-MXene；
(3) Cooling the two-dimensional layered structure compound to room temperature to obtain black suspension, sequentially centrifuging, washing, centrifuging again, and drying to obtain layered V2C-MXene nano materialFeeding;
step two: preparation of V2C-MXene/cobalt-nickel double metal hydroxide composite material
(1) According to the mass ratio, nickel nitrate hexahydrate solution: cobalt nitrate hexahydrate solution: urea solution: v2C-MXene: citric acid solution 1: (0.2-0.6): (1.2-1.6): (0.12-0.45): (0.07-0.16), the solid-to-liquid ratio is 1: (15-20) preparing materials, wherein the cobalt nitrate hexahydrate solution, the nickel nitrate hexahydrate solution, the urea solution and the citric acid solution are calculated according to the mass of the solute;
(2) ultrasonically dispersing a cobalt nitrate hexahydrate solution, a nickel nitrate hexahydrate solution and a urea solution in deionized water to obtain a uniformly dispersed light green mixed solution, and slowly adding V into the mixed solution2C-MXene and citric acid solution are stirred uniformly, wherein citric acid is used as a surfactant;
(3) transferring the mixed solution into a high-pressure reaction kettle, placing the high-pressure reaction kettle in a forced air drying oven for hydrothermal reaction, wherein the hydrothermal reaction time is 6-13h, the reaction temperature is 80-150 ℃, and the cobalt-nickel double metal hydroxide is subjected to hydrothermal reaction in a V state2In-situ growth of C-MXene surface, centrifugal drying of black suspension after reaction to obtain V2C-MXene/cobalt nickel double metal hydroxide composite material.
In the step one (1), preferably, the ratio by volume of the hydrochloric acid solution: sodium fluoride solution 2: 1.
In the step one (1), the stirring time is 10-30min, and the stirring speed is 400-800 rpm.
In the step one (2), in the hydrothermal reaction process, the fluorine ions in the mixed solution can etch away V under the acidic condition2Al layer atoms in the AlC, thereby forming a two-dimensional layered structure with an accordion-like appearance.
In the step one (3), the centrifugation, washing, secondary centrifugation and drying processes of the black suspension are specifically operated as follows: after multiple centrifugation, a black precipitate was obtained and washed with dilute hydrochloric acid to remove residual sodium fluoride. Then washing for several times by adopting absolute ethyl alcohol and deionized water until the solution is neutral, and then centrifuging for several times to obtain a black product V2C-MXene，Transferring the product to a vacuum drying oven for drying for 12h to obtain the required layered V2C-MXene nano material.
In the step one (3), the centrifugation time is 10-30min, and the centrifugation speed is 3000-;
in the first step (3), the drying temperature is 40-100 ℃, and the drying time is 6-12 h;
in the step one (3), the centrifugal cleaning is carried out by using dilute hydrochloric acid, and the concentration of the dilute hydrochloric acid is 0.1-1 mol/L.
In the step one (3), the surface of the prepared two-dimensional layered structure compound is provided with a large number of functional groups such as-OH, -Cl, and-F, and the like, so that V2C-MXene itself exhibits electronegativity.
In the second step (1), the concentration of the cobalt nitrate hexahydrate solution is 0.04-0.1mol/L, the concentration of the nickel nitrate hexahydrate solution is 0.02-0.06mol/L, the concentration of the urea solution is 0.2-0.6mol/L, and the concentration of the citric acid solution is 0.005-0.015 mol/L.
In the second step (2), the ultrasonic time is 1-3h, and the ultrasonic power is 100-500W.
In the second step (3), the cobalt ions and the nickel ions are positively charged, so that the cobalt ions and the nickel ions can be adsorbed on V with a large number of functional groups such as-OH, -Cl and-F under the electrostatic action2C-MXene material surface and in-situ growth are carried out, and finally V2Forming in-situ grown lamellar cobalt-nickel double hydroxide on the surface of the C-MXene to obtain V with a cross-linked structure2C-MXene/cobalt nickel double metal hydroxide composite material.
In the second step (3), the centrifugation time is 10-30min, and the centrifugation speed is 3000-.
In the second step (3), the drying time is 40-100 ℃, and the drying time is 6-12 h.
In the second step (3), prepared V2The specific surface area of the C-MXene/cobalt-nickel double metal hydroxide composite material is 50.25-70.00m2·g-1When the material is used for the cathode of a lithium ion battery, the material is tested to be 100 mA.g-1The first charge-discharge specific capacity under the current density can reach 503.2-556.3 mA.g-1Specific discharge capacity retention rate after 100 cyclesThe content is 81-85%. And has good conductivity and charge transfer resistance of 300-350 omega.
In said step two (3), preferably, V is prepared2The specific surface area of the C-MXene/cobalt-nickel double metal hydroxide composite material can reach 67.25-70.00m2·g-1When the material is used for the cathode of a lithium ion battery, the material is tested to be 100 mA.g-1The first charge-discharge specific capacity under the current density can reach 545.6-556.3 mA.g-1And the retention rate of the discharge specific capacity after 100 times of circulation is 84-85%. And has good conductivity, and the charge transfer resistance is 300-305 omega.
In the second step (3), prepared V2When the C-MXene/cobalt-nickel double metal hydroxide composite material is used for a lithium ion battery cathode, the corresponding cathode material preparation process comprises the steps of dissolving the prepared active substance material, conductive carbon black and polyvinylidene fluoride (PVDF) in a mass ratio of 8:1:1 in N-methyl-2-pyrrolidone (NMP) to form slurry, uniformly stirring, coating the slurry on a copper foil, drying in vacuum, cutting into an electrode slice, using a metal lithium slice as a counter electrode and 1MLiPF6(EC: DC ═ 1:1) as an electrolyte, a polypropylene porous membrane as a separator, and a current density of 100mA · g at the time of test-1The voltage window is 0.01-3V.
The invention has the beneficial effects that:
firstly, the invention adopts a one-step hydrothermal method to realize the high specific capacity cobalt-nickel bimetal hydroxide in V2In-situ growth of C-MXene nanosheet surface, forming alternately stacked V by electrostatic interaction2C-MXene/cobalt nickel double metal hydroxide composite material. The material effectively makes up for V2The C-MXene material has low theoretical capacity, solves the problems of poor conductivity and poor structural stability of the cobalt-nickel double metal hydroxide, and greatly improves the specific capacity and the cycling stability of the lithium ion battery cathode material.
Secondly, the invention utilizes V2The excellent structural stability of C-MXene successfully inhibits the structural collapse caused by volume expansion in the charge-discharge process when the cobalt-nickel double hydroxide is used as the lithium ion battery cathode, and greatly improves the conductivity of the material.
Thirdly, adopting cobalt-nickel metal ions in V2The method for the in-situ growth of the surface of the C-MXene is simple and convenient to operate and easy to realize. And V formed2The alternating stack structure of C-MXene and cobalt-nickel double metal hydroxide has larger specific surface area (more than 50 m)2·g-1) When the lithium ion battery cathode is used as a lithium ion battery cathode, intercalation sites of lithium ions can be increased so as to improve electrochemical performance.
The product obtained by the method is dispersed and does not agglomerate, and the selected etching agents are hydrochloric acid and sodium fluoride, so that the cost is lower, the safety and the environmental protection are better, and the overall preparation process has good realizability compared with the traditional hydrofluoric acid etching.
Description of the drawings:
FIG. 1 is V prepared in example 32SEM topography of the C-MXene/cobalt nickel double metal hydroxide composite material;
FIG. 2 is V prepared in example 32XRD pattern of C-MXene/cobalt nickel double metal hydroxide composite material;
FIG. 3 is V prepared in example 32A nitrogen adsorption and desorption curve of the C-MXene/cobalt-nickel double metal hydroxide composite material;
FIG. 4 is V prepared in example 32C-MXene/cobalt nickel double metal hydroxide composite material constant current charge-discharge curve;
FIG. 5 is V prepared in example 32A cycle stability curve of the C-MXene/cobalt-nickel double metal hydroxide composite material;
FIG. 6 is V prepared in example 32C-MXene/cobalt nickel double hydroxide composite material alternating current impedance diagram.
The specific implementation mode is as follows:
the present invention will be described in further detail with reference to examples.
In the following examples:
the adding mass of the nickel nitrate hexahydrate solution, the cobalt nitrate hexahydrate solution, the urea solution and the citric acid solution is calculated by the mass of the solute.
Prepared V2Application of C-MXene/cobalt-nickel double metal hydroxide composite material in lithium ion batteryIn the negative electrode, the corresponding negative electrode material preparation process comprises the steps of dissolving the prepared active substance material, conductive carbon black and polyvinylidene fluoride (PVDF) in N-methyl-2-pyrrolidone (NMP) according to the mass ratio of 8:1:1 to form slurry, uniformly stirring, coating the slurry on copper foil, drying in vacuum, cutting into electrode plates, and using a metal lithium sheet as a counter electrode to obtain 1MLiPF6(EC: DC ═ 1:1) as an electrolyte, a polypropylene porous membrane as a separator, and a current density of 100mA · g at the time of test-1The voltage window is 0.01-3V.
Example 1
The method comprises the following steps: preparation of layer V2C-MXene nano material
Firstly, the volume ratio of hydrochloric acid solution: sodium fluoride solution ═ 1: 2, adding 3mol/L sodium fluoride solution into 36mL of 32 wt% hydrochloric acid, stirring uniformly, and then according to the weight ratio of the aluminum vanadium carbide solution: the volume ratio of (sodium fluoride solution + hydrochloric acid solution) is 1: 15, 2.5mol/L of aluminum vanadium carbide is added, and the mixture is stirred at 400rpm for 10 minutes to obtain a uniformly dispersed black mixed solution. Then, the mixed solution was transferred to a high-pressure reaction vessel, and placed in a thermostat to undergo hydrothermal reaction at 80 ℃ for 60 hours.
After the reaction time is over, taking out the high-pressure reaction kettle, naturally cooling to room temperature, centrifuging the obtained black suspension, washing with dilute hydrochloric acid, then centrifuging and washing with absolute ethyl alcohol and deionized water for a plurality of times until the pH of the solution is 7, and drying the obtained black product at 40 ℃ for 6 hours in vacuum to obtain the layered V2C-MXene nano material.
Step two: preparation of V2C-MXene/cobalt-nickel double metal hydroxide composite material
According to the mass ratio, nickel nitrate hexahydrate solution: cobalt nitrate hexahydrate solution: urea solution: v2C-MXene: citric acid solution 1: 0.2: 1.2: 0.12: 0.07, the solid-to-liquid ratio is 1: and 15, preparing the materials. The concentration of cobalt nitrate hexahydrate is 0.04mol/L, the concentration of nickel nitrate hexahydrate is 0.02mol/L, the concentration of urea solution is 0.2mol/L, and the concentration of citric acid solution is 0.005mol/L, the cobalt nitrate hexahydrate, the nickel nitrate hexahydrate and the urea solution are ultrasonically dispersed in 31mL of deionized water to obtain a uniformly dispersed light green mixed solution, and then the light green mixed solution is slowly dispersedAdding V2C-MXene and citric acid solution are stirred uniformly. The mixed solution was transferred to an autoclave and placed in a thermostat to undergo hydrothermal reaction at 80 ℃ for 6 hours. After the reaction is finished, washing the obtained black suspension for a plurality of times by adopting absolute ethyl alcohol and deionized water, centrifuging, and drying the obtained black precipitate for 6 hours in vacuum at the temperature of 40 ℃ to obtain V2C-MXene/cobalt nickel double metal hydroxide composite material.
Will V2The negative plate is made of the C-MXene/cobalt-nickel double metal hydroxide composite material, metal lithium is used as a positive electrode, EC/EMC solution of 1M lithium hexafluorophosphate is used as electrolyte, and the CR2032 button lithium ion battery is assembled for carrying out charge and discharge tests of the battery. The specific surface area of the material is 50.35m when the material is used as a lithium ion battery cathode material2·g-1The first discharge specific capacity is 503.2 mAh.g-1After 100 cycles, the discharge specific capacity retention rate is 81%, and the charge transfer impedance is 350 omega.
Example 2
The method comprises the following steps: preparation of layer V2C-MXene nano material
Firstly, the volume ratio of hydrochloric acid: sodium fluoride ═ 1.5: 2, adding 4mol/L sodium fluoride solution into 38mL of 34 wt% hydrochloric acid, stirring uniformly, and then according to the weight ratio of the aluminum vanadium carbide solution: the volume ratio of (sodium fluoride solution + hydrochloric acid solution) is 1: 18 adding 4mol/L of aluminum vanadium carbide, and stirring at 500rpm for 20 minutes to obtain a uniformly dispersed black mixed solution. Thereafter, the mixed solution was transferred to a high-pressure reaction vessel, and placed in a thermostat to undergo hydrothermal reaction at 70 ℃ for 65 hours.
After the reaction time is over, taking out the high-pressure reaction kettle, naturally cooling to room temperature, centrifuging the obtained black suspension, washing with dilute hydrochloric acid, then centrifuging and washing with absolute ethyl alcohol and deionized water for a plurality of times until the pH of the solution is 7, and drying the obtained black product at 50 ℃ for 8 hours in vacuum to obtain the layered V2C-MXene nano material.
Step two: preparation of V2C-MXene/cobalt-nickel double metal hydroxide composite material
According to the mass ratio, nickel nitrate hexahydrate solution: cobalt nitrate hexahydrate solution: urea solution: v2C-MXene: citric acid solution 1: 0.35: 1.34: 0.22: 0.1, the solid-to-liquid ratio is 1: and 16, preparing materials. The concentration of cobalt nitrate hexahydrate is 0.04mol/L, the concentration of nickel nitrate hexahydrate is 0.02mol/L, the concentration of urea solution is 0.2mol/L, and the concentration of citric acid solution is 0.005mol/L, the cobalt nitrate hexahydrate, the nickel nitrate hexahydrate and the urea solution are ultrasonically dispersed in 58mL of deionized water to obtain uniformly dispersed light green mixed solution, and then V is slowly added2C-MXene and citric acid solution are stirred uniformly. The mixed solution was transferred to an autoclave and placed in a thermostat to conduct hydrothermal reaction at 115 ℃ for 10 hours. After the reaction is finished, washing the obtained black suspension by adopting absolute ethyl alcohol and deionized water, centrifuging for a plurality of times, and drying the obtained black precipitate in vacuum at 60 ℃ for 12h to obtain V2The test shows that the C-MXene/cobalt-nickel double metal hydroxide composite material as the negative electrode material of the lithium ion battery has the specific surface area of 58.85m2·g-1The first discharge specific capacity is 513.8mAh g-1The discharge specific capacity retention rate after 100 cycles is 83%, and the charge transfer resistance is 333 omega.
Example 3
The method comprises the following steps: preparation of layer V2C-MXene nano material
Firstly, the volume ratio of hydrochloric acid: sodium fluoride ═ 2:1, adding 6mol/L sodium fluoride solution into 40mL of 38 wt% hydrochloric acid, stirring uniformly, and then according to the weight ratio of aluminum vanadium carbide solution: the volume ratio of (sodium fluoride solution + hydrochloric acid solution) is 1: 6mol/L of aluminum vanadium carbide was added to the solution 20, and the mixture was stirred at 500rpm for 20 minutes to obtain a uniformly dispersed black mixed solution. Thereafter, the mixed solution was transferred to a high-pressure reaction vessel and put into a thermostat to perform hydrothermal reaction at 90 ℃ for 72 hours.
After the reaction time is over, taking out the high-pressure reaction kettle, naturally cooling to room temperature, centrifuging the obtained black suspension, washing with dilute hydrochloric acid, then centrifuging and washing with absolute ethyl alcohol and deionized water for a plurality of times until the pH of the solution is 7, and drying the obtained black product at 80 ℃ for 10 hours in vacuum to obtain the layered V2C-MXene nano material.
Step two: preparation of V2C-MXene/Cobalt-nickel double metal hydroxide composite material
According to the mass ratio, nickel nitrate hexahydrate solution: cobalt nitrate hexahydrate solution: urea solution: v2C-MXene: citric acid solution 1: 0.42: 1.55: 0.31: 0.12, the solid-to-liquid ratio is 1: and 18, preparing materials. The concentration of a cobalt nitrate hexahydrate solution is 0.06mol/L, the concentration of a nickel nitrate hexahydrate solution is 0.04mol/L, the concentration of a urea solution is 0.4mol/L, and the concentration of a citric acid solution is 0.01mol/L, the cobalt nitrate hexahydrate solution, the nickel nitrate hexahydrate solution and the urea solution are ultrasonically dispersed in 60mL of deionized water to obtain a uniformly dispersed light green mixed solution, and then V is slowly added2C-MXene citric acid solution and stirring uniformly. The mixed solution was transferred to an autoclave and placed in a thermostat to undergo hydrothermal reaction at 120 ℃ for 12 hours. After the reaction is finished, washing the obtained black suspension by adopting absolute ethyl alcohol and deionized water, centrifuging for a plurality of times, and drying the obtained black precipitate for 10 hours in vacuum at 80 ℃ to obtain V2C-MXene/cobalt nickel double metal hydroxide composite material.
FIG. 1 shows V prepared in this example2SEM (scanning electron microscope) morphology of C-MXene/cobalt-nickel double-metal hydroxide composite material, and from the SEM morphology, in-situ growth of cobalt-nickel double-metal hydroxide nanosheets on V with lamellar structure2C-MXene surface. FIG. 2 is V2The XRD pattern of the C-MXene/cobalt nickel double metal hydroxide composite material can be seen to have V simultaneously2The diffraction peaks of C-MXene, cobalt hydroxide and nickel hydroxide show that the cobalt-nickel double-metal hydroxide nanosheet is V2And (3) in-situ growth of the surface of the C-MXene. FIG. 3 is V2The nitrogen adsorption and desorption curve of the C-MXene/cobalt-nickel double metal hydroxide composite material can be seen from the figure, and V can be seen2The specific surface area of the C-MXene/cobalt-nickel double metal hydroxide composite material is 68.75m2·g-1. FIG. 4 is V2The constant current charge-discharge curve of the C-MXene/cobalt-nickel double metal hydroxide composite material shows that the first charge-discharge specific capacity can reach 548.8mAh g-1. FIG. 5 is V2The cycle stability curve of the C-MXene/cobalt-nickel double metal hydroxide composite material can be seen as V2C-MXene/cobalt-nickel bimetalThe hydroxide composite material still has 84% capacity retention rate after being cycled for 100 times, and shows good cycle performance. FIG. 6 is V2The AC impedance diagram of the C-MXene/cobalt-nickel double metal hydroxide composite material can be seen, and V can be seen from the diagram2The charge transfer resistance of the C-MXene/cobalt-nickel double metal hydroxide composite material is 303 omega, and excellent conductivity is shown.
Comparative example 3-1
The step is the same as the embodiment 3, and the difference is that the cobalt-nickel double metal hydroxide is prepared in the step two, and the specific process is as follows: first, 25ml of 0.1M Co (NO)3)2·6H2The O methanol solution was added to 25ml of a methanol solution containing 20 g/L2-methylimidazole, stirred for 30 seconds, magnetically stirred for 30 minutes, then the mixed solution was allowed to stand for 12 hours, and the mixture was centrifuged and washed with methanol several times. Dispersing 30mg of the above ZIF-67 in 20ml of ethanol, and then adding 10mg/ml of Ni (NO) under magnetic stirring3)2Ethanol solution, and stirring for ten minutes. Finally, washing the product with ethanol for 3 times, and drying in a vacuum oven at room temperature for 24h to obtain cobalt-nickel double hydroxide, and mixing with the cobalt-nickel double hydroxide to obtain the product V2Mixing the C-MXene nano materials, and carrying out hydrothermal reaction under the same conditions to obtain the product. The detection result shows that the cobalt-nickel double metal hydroxide is not realized in V2The growth of the surface of C, the microscopic result state is that the size of the cobalt-nickel double metal hydroxide lamella is too large to be inserted into V2And the interlayer C does not realize lamellar adsorption, has poor performance and lower specific discharge capacity than a product obtained by in-situ growth by adopting a one-step hydrothermal method.
Comparative examples 3 to 2
The second step is the same as the embodiment 3, except that HF is used as an etchant in the first step, and the specific process is as follows: first, 40mL of 30 wt% hydrochloric acid was added and stirred uniformly, and then 6mol/L of V was slowly added2And AlC, stirring at 500rpm for 20 minutes to obtain a uniformly dispersed black mixed solution. Thereafter, the mixed solution was transferred to a high-pressure reaction vessel and put into a thermostat to perform hydrothermal reaction at 90 ℃ for 72 hours. After detection, V is not realized2Etching of AlC, microscopic results not observedAccordion-like structures.
Comparative examples 3 to 3
Similar to example 3, except that the sodium fluoride solution in the etching acid was completely replaced with the hydrochloric acid solution of the same volume, and it was determined that V was not achieved2The microscopic result of AlC etching is that no accordion-shaped structure is observed, and the normal charging and discharging process can not be carried out after the battery is assembled.
Comparative examples 3 to 4
Similar to example 3, except that the hydrochloric acid solution in the etching acid was completely replaced with an equal volume of sodium fluoride solution, it was determined that V was not achieved2The microscopic result of AlC etching is that no accordion-shaped structure is observed, and the normal charging and discharging process can not be carried out after the battery is assembled.
Example 4
The method comprises the following steps: preparation of layer V2C-MXene nano material
Firstly, the volume ratio of hydrochloric acid: sodium fluoride ═ 2:1, adding 4.5mol/L sodium fluoride solution into 40mL of 35 wt% hydrochloric acid, stirring uniformly, and then according to the weight ratio of aluminum vanadium carbide solution: the volume ratio of (sodium fluoride solution + hydrochloric acid solution) is 1: 4mol/L of aluminum vanadium carbide was added to the solution 20, and the mixture was stirred at 500rpm for 20 minutes to obtain a uniformly dispersed black mixed solution. Thereafter, the mixed solution was transferred to a high-pressure reaction vessel and put into a thermostat to perform hydrothermal reaction at 90 ℃ for 72 hours.
After the reaction time is over, taking out the high-pressure reaction kettle, naturally cooling to room temperature, centrifuging the obtained black suspension, washing with dilute hydrochloric acid, then centrifuging and washing with absolute ethyl alcohol and deionized water for a plurality of times until the pH of the solution is 7, and drying the obtained black product at 80 ℃ for 10 hours in vacuum to obtain the layered V2C-MXene nano material.
Step two: preparation of V2C-MXene/cobalt-nickel double metal hydroxide composite material
According to the mass ratio, nickel nitrate hexahydrate solution: cobalt nitrate hexahydrate solution: urea solution: v2C-MXene: citric acid solution 1: 0.42: 1.55: 0.31: 0.12, the solid-to-liquid ratio is 1: and 18, preparing materials. The concentration of the cobalt nitrate hexahydrate solution is 0.06mol/L and the concentration of the nickel nitrate hexahydrate solution is 0.04molPerforming ultrasonic dispersion on a cobalt nitrate hexahydrate solution, a nickel nitrate hexahydrate solution and a urea solution together to obtain a uniformly dispersed light green mixed solution, wherein the concentration of the urea solution is 0.4mol/L and the concentration of the citric acid solution is 0.01mol/L, and then slowly adding V2C-MXene citric acid solution and stirring uniformly. The mixed solution was transferred to an autoclave and placed in a thermostat to undergo hydrothermal reaction at 120 ℃ for 12 hours. After the reaction is finished, washing the obtained black suspension by adopting absolute ethyl alcohol and deionized water, centrifuging for a plurality of times, and drying the obtained black precipitate for 10 hours in vacuum at 80 ℃ to obtain V2The test shows that the C-MXene/cobalt-nickel double metal hydroxide composite material as the negative pole material of lithium ion battery has a specific surface area of 70.00m2·g-1The first discharge specific capacity is 556.3mAh g-1The discharge specific capacity retention rate after 100 cycles is 85%, and the charge transfer impedance is 300 omega.
Example 5
The method comprises the following steps: preparation of layer V2C-MXene nano material
Firstly, the volume ratio of hydrochloric acid: sodium fluoride ═ 2:1, adding 3mol/L sodium fluoride solution into 40mL of 32 wt% hydrochloric acid, stirring uniformly, and then according to the weight ratio of aluminum vanadium carbide solution: the volume ratio of (sodium fluoride solution + hydrochloric acid solution) is 1: 2.5mol/L of vanadium aluminum carbide was added to the solution, and the mixture was stirred at 500rpm for 20 minutes to obtain a uniformly dispersed black mixed solution. Thereafter, the mixed solution was transferred to a high-pressure reaction vessel and put into a thermostat to perform hydrothermal reaction at 90 ℃ for 72 hours.
After the reaction time is over, taking out the high-pressure reaction kettle, naturally cooling to room temperature, centrifuging the obtained black suspension, washing with dilute hydrochloric acid, then centrifuging and washing with absolute ethyl alcohol and deionized water for a plurality of times until the pH of the solution is 7, and drying the obtained black product at 80 ℃ for 10 hours in vacuum to obtain the layered V2C-MXene nano material.
Step two: preparation of V2C-MXene/cobalt-nickel double metal hydroxide composite material
According to the mass ratio, nickel nitrate hexahydrate solution: cobalt nitrate hexahydrate solution: urea solution: v2C-MXene: lemonAcid solution 1: 0.42: 1.55: 0.31: 0.12, the solid-to-liquid ratio is 1: and 18, preparing materials. The concentration of a cobalt nitrate hexahydrate solution is 0.06mol/L, the concentration of a nickel nitrate hexahydrate solution is 0.04mol/L, the concentration of a urea solution is 0.4mol/L, and the concentration of a citric acid solution is 0.01mol/L, the cobalt nitrate hexahydrate solution, the nickel nitrate hexahydrate solution and the urea solution are ultrasonically dispersed in 60mL of deionized water to obtain a uniformly dispersed light green mixed solution, and then V is slowly added2C-MXene citric acid solution and stirring uniformly. The mixed solution was transferred to an autoclave and placed in a thermostat to undergo hydrothermal reaction at 120 ℃ for 12 hours. After the reaction is finished, washing the obtained black suspension by adopting absolute ethyl alcohol and deionized water, centrifuging for a plurality of times, and drying the obtained black precipitate for 10 hours in vacuum at 80 ℃ to obtain V2The test shows that the C-MXene/cobalt-nickel double metal hydroxide composite material as the negative electrode material of the lithium ion battery has the specific surface area of 67.25m2·g-1The first discharge specific capacity is 545.6mAh g-1After 100 cycles, the discharge specific capacity retention rate is 84%, and the charge transfer impedance is 305 omega.
Example 6
The method comprises the following steps: preparation of layer V2C-MXene nano material
Firstly, the volume ratio of hydrochloric acid: sodium fluoride ═ 3: 1, adding 5mol/L sodium fluoride solution into 38mL of 36 wt% hydrochloric acid, stirring uniformly, and then according to the weight ratio of aluminum vanadium carbide solution: the volume ratio of (sodium fluoride solution + hydrochloric acid solution) is 1: 25 adding 5mol/L of aluminum vanadium carbide, and stirring at 800rpm for 30 minutes to obtain a uniformly dispersed black mixed solution. Then, the mixed solution was transferred to a high-pressure reaction vessel and put into a thermostat to perform hydrothermal reaction at 120 ℃ for 90 hours.
After the reaction time is over, taking out the high-pressure reaction kettle, naturally cooling to room temperature, centrifuging the obtained black suspension, washing with dilute hydrochloric acid, then centrifuging and washing with absolute ethyl alcohol and deionized water for a plurality of times until the pH of the solution is 7, and drying the obtained black product at 100 ℃ in vacuum for 12 hours to obtain the layered V2C-MXene nano material.
Step two: preparation of V2C-MXene/cobalt-nickel double metal hydroxide complexComposite material
According to the mass ratio, nickel nitrate hexahydrate solution: cobalt nitrate hexahydrate solution: urea solution: v2C-MXene: citric acid solution 1: 0.6: 1.6: 0.45: 0.16, solid-to-liquid ratio of 1: and 20, preparing the materials. The concentration of cobalt nitrate hexahydrate is 0.1mol/L, the concentration of nickel nitrate hexahydrate is 0.06mol/L, the concentration of urea solution is 0.6mol/L, and the concentration of citric acid solution is 0.015mol/L, the cobalt nitrate hexahydrate, the nickel nitrate hexahydrate and the urea are ultrasonically dispersed in 81mL of deionized water to obtain a uniformly dispersed light green mixed solution, and then V is slowly added2C-MXene and citric acid are stirred uniformly. The mixed solution was transferred to an autoclave and placed in a thermostat to undergo hydrothermal reaction at 150 ℃ for 13 hours. After the reaction is finished, washing the obtained black suspension by adopting absolute ethyl alcohol and deionized water, centrifuging for a plurality of times, and drying the obtained black precipitate in vacuum at 100 ℃ for 12h to obtain V2The test shows that the C-MXene/cobalt-nickel double metal hydroxide composite material as the negative electrode material of the lithium ion battery has the specific surface area of 57.65m2·g-1The first discharge specific capacity is 530.8mAh g-1The discharge specific capacity retention rate after 100 cycles was 83%, and the charge transfer resistance was 321 Ω.
Example 7
The method comprises the following steps: preparation of layer V2C-MXene nano material
Firstly, the volume ratio of hydrochloric acid: sodium fluoride ═ 1:1, adding 6mol/L sodium fluoride solution into 40mL of 38 wt% hydrochloric acid, stirring uniformly, and then according to the weight ratio of aluminum vanadium carbide solution: the volume ratio of (sodium fluoride solution + hydrochloric acid solution) is 1: 6mol/L of aluminum vanadium carbide was added to the solution, and the mixture was stirred at 800rpm for 30 minutes to obtain a uniformly dispersed black mixed solution. Then, the mixed solution was transferred to a high-pressure reaction vessel and put into a thermostat to perform hydrothermal reaction at 120 ℃ for 90 hours.
After the reaction time is over, taking out the high-pressure reaction kettle, naturally cooling to room temperature, centrifuging the obtained black suspension, washing with dilute hydrochloric acid, then centrifuging and washing with absolute ethyl alcohol and deionized water for a plurality of times until the pH of the solution is 7, and drying the obtained black product at 80 ℃ in vacuum for 12 hours to obtain the layered V2C-MXene nano material.
Step two: preparation of V2C-MXene/cobalt-nickel double metal hydroxide composite material
According to the mass ratio, nickel nitrate hexahydrate solution: cobalt nitrate hexahydrate solution: urea solution: v2C-MXene: citric acid solution 1: 0.6: 1.6: 0.45: 0.16, solid-to-liquid ratio of 1: and 20, preparing the materials. The concentration of a cobalt nitrate hexahydrate solution is 0.1mol/L, the concentration of a nickel nitrate hexahydrate solution is 0.06mol/L, the concentration of a urea solution is 0.6mol/L, and the concentration of a citric acid solution is 0.015mol/L, the cobalt nitrate hexahydrate solution, the nickel nitrate hexahydrate solution and the urea solution are ultrasonically dispersed in 81mL of deionized water to obtain a uniformly dispersed light green mixed solution, and then V is slowly added2C-MXene and citric acid solution are stirred uniformly. The mixed solution was transferred to an autoclave and placed in a thermostat to undergo hydrothermal reaction at 150 ℃ for 13 hours. After the reaction is finished, washing the obtained black suspension by adopting absolute ethyl alcohol and deionized water, centrifuging for a plurality of times, and drying the obtained black precipitate in vacuum at 100 ℃ for 12h to obtain V2The test shows that the C-MXene/cobalt-nickel double metal hydroxide composite material as the negative electrode material of the lithium ion battery has the specific surface area of 58.35m2·g-1The first discharge specific capacity is 527.1mAh g-1The discharge specific capacity retention rate after 100 cycles is 82%, and the charge transfer impedance is 315 omega.
Claims (8)
1. V-shaped groove2The preparation method of the C-MXene/cobalt-nickel double metal hydroxide composite material is characterized by comprising the following steps:
the method comprises the following steps: preparation of layer V2C-MXene nano material
(1) According to volume ratio, hydrochloric acid solution: sodium fluoride solution ═ (1-3): 1, adding sodium fluoride solution into hydrochloric acid solution, stirring to obtain uniform hydrochloric acid and sodium fluoride mixed solution, and then slowly adding V2Continuously stirring the AlC solution to obtain a uniformly dispersed black mixed solution, wherein the concentration of the sodium fluoride solution is 3-6mol/L, the concentration of the aluminum vanadium carbide solution is 2.5-6mol/L, the mass fraction of the hydrochloric acid solution is 32-38 wt%, and V is the volume ratio of V to V2AlC solution: (sodium fluoride solution + hydrochloric acid solution) ═ 1: (15-25);
(2) carrying out hydrothermal reaction on the mixed solution, wherein the hydrothermal reaction time is 60-90h, the reaction temperature is 80-120 ℃, and obtaining a two-dimensional layered structure compound V2C-MXene；
(3) Cooling the two-dimensional layered structure compound to room temperature to obtain black suspension, sequentially centrifuging, washing, centrifuging again, and drying to obtain layered V2C-MXene nano material;
step two: preparation of V2C-MXene/cobalt-nickel double metal hydroxide composite material
(1) According to the mass ratio, nickel nitrate hexahydrate solution: cobalt nitrate hexahydrate solution: urea solution: v2C-MXene: citric acid solution 1: (0.2-0.6): (1.2-1.6): (0.12-0.45): (0.07-0.16), the solid-to-liquid ratio is 1: (15-20) preparing materials, wherein the adding amounts of the cobalt nitrate hexahydrate solution, the nickel nitrate hexahydrate solution, the urea solution and the citric acid solution are calculated according to the mass of the solute;
(2) ultrasonically dispersing a cobalt nitrate hexahydrate solution, a nickel nitrate hexahydrate solution and a urea solution in deionized water to obtain a uniformly dispersed light green mixed solution, and slowly adding V into the mixed solution2C-MXene and citric acid solution are uniformly stirred to obtain mixed solution;
(3) carrying out hydrothermal reaction on the mixed solution, wherein the hydrothermal reaction time is 6-13h, the reaction temperature is 80-150 ℃, and the cobalt-nickel double hydroxide is obtained at V2In-situ growth of C-MXene surface, centrifugal drying of black suspension after reaction to obtain V2C-MXene/cobalt nickel double metal hydroxide composite material.
2. V according to claim 12The preparation method of the C-MXene/cobalt-nickel double metal hydroxide composite material is characterized in that in the step one (1), the volume ratio of hydrochloric acid solution: sodium fluoride solution 2: 1.
3. V according to claim 12Preparation method of C-MXene/cobalt-nickel double metal hydroxide composite materialCharacterized in that in the step one (1), the stirring time is 10-30min, and the stirring speed is 400-800 rpm.
4. V according to claim 12The preparation method of the C-MXene/cobalt-nickel double metal hydroxide composite material is characterized in that in the step one (3): the centrifugation time is 10-30min, and the centrifugation speed is 3000-; the drying temperature is 40-100 deg.C, and the drying time is 6-12 h.
5. V according to claim 12The preparation method of the C-MXene/cobalt-nickel double metal hydroxide composite material is characterized in that in the second step (1), the concentration of the cobalt nitrate hexahydrate solution is 0.04-0.1mol/L, the concentration of the nickel nitrate hexahydrate solution is 0.02-0.06mol/L, the concentration of the urea solution is 0.2-0.6mol/L, and the concentration of the citric acid solution is 0.005-0.015 mol/L.
6. V according to claim 12The preparation method of the C-MXene/cobalt-nickel double metal hydroxide composite material is characterized in that in the second step (2), the ultrasonic time is 1-3h, and the ultrasonic power is 100-500W.
7. V according to claim 12The preparation method of the C-MXene/cobalt-nickel double metal hydroxide composite material is characterized in that in the second step (3): the centrifugation time is 10-30min, and the centrifugation speed is 3000-; the drying time is 40-100 deg.C, and the drying time is 6-12 h.
8. V according to claim 12The preparation method of the C-MXene/cobalt-nickel double metal hydroxide composite material is characterized in that in the second step (3), V is prepared2The specific surface area of the C-MXene/cobalt-nickel double metal hydroxide composite material is 50.25-70.00m2·g-1When the material is used for the cathode of a lithium ion battery, the material is tested to be 100 mA.g-1The first charge-discharge specific capacity under the current density can reach 503.2-556.3 mA.g-1The discharge specific capacity retention rate is 81-85% after 100 times of circulation, and charge transfer is performedThe resistance is 300-350 omega.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113921817A (en) * | 2021-08-23 | 2022-01-11 | 济南大学 | V-shaped groove3S4@V2C composite material and preparation method and application thereof |
| CN114823168A (en) * | 2022-04-13 | 2022-07-29 | 齐齐哈尔大学 | V-shaped groove 2 CT x Preparation method and application of/NiV-LDH composite material |
| CN114883541A (en) * | 2022-04-24 | 2022-08-09 | 北京科技大学 | Fe 7 S 8 @V 2 Preparation method of C @ C high-rate sodium storage electrode material |
| CN115528227A (en) * | 2022-09-27 | 2022-12-27 | 南通大学 | Preparation method of bimetallic CoZn-Se @ MXene electrode |
| CN115663129A (en) * | 2022-09-30 | 2023-01-31 | 济南大学 | Phosphorus-doped two-dimensional layered vanadium carbide and nickel-cobalt layered double hydroxide composite electrode material and preparation method thereof |
| CN117153578A (en) * | 2023-09-11 | 2023-12-01 | 哈尔滨师范大学 | Cobalt ion intercalated vanadium carbide nano-sheet and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108346519A (en) * | 2018-01-26 | 2018-07-31 | 陕西科技大学 | A kind of MXene- hydroxyl modifieds titanium carbide ultrathin nanometer band and its floride-free synthetic method |
| CN108525647A (en) * | 2018-04-12 | 2018-09-14 | 华东交通大学 | Biomass carbon/copper magnalium ternary metal hydroxide denitrogenates phosphate material preparation method |
| CN110118814A (en) * | 2019-05-10 | 2019-08-13 | 重庆大学 | The Ni-based layered double-hydroxide composite material and preparation method of MXene/ |
| CN110942921A (en) * | 2019-11-26 | 2020-03-31 | 北京科技大学 | Preparation method of novel three-dimensional composite aerogel electrode material |
| US20200399771A1 (en) * | 2019-06-24 | 2020-12-24 | The Hong Kong Polytechnic University | Method for hf-free facile and rapid synthesis of mxenes related compounds |
| CN112175275A (en) * | 2020-09-29 | 2021-01-05 | 中北大学 | Mike alkene/ethylene-vinyl acetate copolymer flexible sensing material and preparation method thereof |
| CN112467069A (en) * | 2020-12-11 | 2021-03-09 | 燕山大学 | Battery negative electrode material and preparation method and application thereof |
-
2021
- 2021-03-19 CN CN202110294284.XA patent/CN113054187A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108346519A (en) * | 2018-01-26 | 2018-07-31 | 陕西科技大学 | A kind of MXene- hydroxyl modifieds titanium carbide ultrathin nanometer band and its floride-free synthetic method |
| CN108525647A (en) * | 2018-04-12 | 2018-09-14 | 华东交通大学 | Biomass carbon/copper magnalium ternary metal hydroxide denitrogenates phosphate material preparation method |
| CN110118814A (en) * | 2019-05-10 | 2019-08-13 | 重庆大学 | The Ni-based layered double-hydroxide composite material and preparation method of MXene/ |
| US20200399771A1 (en) * | 2019-06-24 | 2020-12-24 | The Hong Kong Polytechnic University | Method for hf-free facile and rapid synthesis of mxenes related compounds |
| CN110942921A (en) * | 2019-11-26 | 2020-03-31 | 北京科技大学 | Preparation method of novel three-dimensional composite aerogel electrode material |
| CN112175275A (en) * | 2020-09-29 | 2021-01-05 | 中北大学 | Mike alkene/ethylene-vinyl acetate copolymer flexible sensing material and preparation method thereof |
| CN112467069A (en) * | 2020-12-11 | 2021-03-09 | 燕山大学 | Battery negative electrode material and preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| WU MENGET AL: "Synthesis and electrochemical properties of V2C MXene by etching in opened/closed environments", 《JOURNAL OF ADVANCED CERAMICS》 * |
| ZHANG RUI ET AL: "NiCo-LDH/Ti3C2 MXene hybrid materials for lithium ion battery with high-rate capability and long cycle life", 《JOURNAL OF ENERGY CHEMISTRY》 * |
| 罗学涛 刘应宽 甘传海: "《锂离子电池用纳米硅及硅碳负极材料》", 31 August 2020 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113921817A (en) * | 2021-08-23 | 2022-01-11 | 济南大学 | V-shaped groove3S4@V2C composite material and preparation method and application thereof |
| CN114823168A (en) * | 2022-04-13 | 2022-07-29 | 齐齐哈尔大学 | V-shaped groove 2 CT x Preparation method and application of/NiV-LDH composite material |
| CN114883541A (en) * | 2022-04-24 | 2022-08-09 | 北京科技大学 | Fe 7 S 8 @V 2 Preparation method of C @ C high-rate sodium storage electrode material |
| CN114883541B (en) * | 2022-04-24 | 2023-04-28 | 北京科技大学 | Fe (Fe) 7 S 8 @V 2 Preparation method of C@C high-rate sodium storage electrode material |
| CN115528227A (en) * | 2022-09-27 | 2022-12-27 | 南通大学 | Preparation method of bimetallic CoZn-Se @ MXene electrode |
| CN115663129A (en) * | 2022-09-30 | 2023-01-31 | 济南大学 | Phosphorus-doped two-dimensional layered vanadium carbide and nickel-cobalt layered double hydroxide composite electrode material and preparation method thereof |
| CN117153578A (en) * | 2023-09-11 | 2023-12-01 | 哈尔滨师范大学 | Cobalt ion intercalated vanadium carbide nano-sheet and preparation method and application thereof |
| CN117153578B (en) * | 2023-09-11 | 2024-03-12 | 哈尔滨师范大学 | Cobalt ion intercalated vanadium carbide nano-sheet and preparation method and application thereof |
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