CN112824323A - Indium-doped zinc oxide composite reduced graphene oxide material, and preparation and application thereof - Google Patents
Indium-doped zinc oxide composite reduced graphene oxide material, and preparation and application thereof Download PDFInfo
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Abstract
The invention relates to a preparation method of an indium-doped zinc oxide composite reduced graphene oxide material and a general method of the indium-doped zinc oxide composite reduced graphene oxide material in application to a cathode of a zinc-nickel secondary battery. According to the invention, indium element is doped into the position of zinc oxide lattice substituted for partial zinc element by using a hydrothermal synthesis method, and simultaneously indium-doped zinc oxide is supported on the sheet layer of reduced graphene oxide in the process. The amount of free electrons in the zinc oxide can be increased by doping the indium element, so that the carrier concentration can be increased, and the conductivity of the material can be enhanced. The resulting composite material has a uniform sheet structure while exhibiting very excellent electrochemical properties. The raw materials are zinc acetate, potassium citrate, urea, a small amount of indium chloride, a small amount of graphite oxide and the like, so that the raw materials are wide in source and low in price, and the electrode material is simple and controllable in preparation process and simple in equipment, and is a method which is easy to produce on a large scale.
Description
Technical Field
The invention relates to a preparation method of an indium-doped zinc oxide composite reduced graphene oxide material and application of the material as a cathode of a zinc-nickel secondary battery, belonging to the field of inorganic nano materials and electrochemistry.
Background
The zinc-nickel secondary battery uses zinc/zinc oxide as a negative electrode and nickel hydroxide/nickel oxyhydroxide as a positive electrode, and has the characteristics of higher specific energy, good safety and low price. Based on the advantages, the zinc-nickel secondary battery is expected to be applied to a power supply, a starting power supply and the like of a small electric vehicle in the future, and is very likely to replace the lead-acid battery using the toxic lead compound at present. Therefore, the research on the zinc-nickel secondary battery and the electrode material thereof is receiving increasing attention.
At present, the main problem encountered in the research of zinc-nickel secondary power supply is that the service life of the battery is short, and the main reason is that the zinc cathode has the problems of dendritic crystal growth, deformation and the like, thereby reducing the utilization rate of active substances and rapidly attenuating the battery capacity. Therefore, the search for negative electrode materials with high specific capacity and long cycle life is the focus of research on zinc-nickel secondary batteries. At present, the research on the negative electrode material of the zinc-nickel secondary battery mainly focuses on the modification research on the discharge state active substance zinc oxide, and the common method adopted for modification comprises a compounding method, such as compounding zinc oxide and polypyrrole, and the specific discharge capacity and the cycling stability of the material are improved by enhancing the conductivity of the material and inhibiting the dissolution of the zinc oxide; morphology and particle size control are also common methods, such as nano zinc oxide preparation and the like, and the cycle life of the zinc oxide material is prolonged by controlling the particle size of the synthesized zinc oxide material to a nano pole so that the zinc oxide material grows epitaxially but not dendrites; meanwhile, the zinc oxide with small particle size has larger specific surface area, which is beneficial to increasing the contact area between the zinc oxide and electrolyte, thereby reducing electrode polarization and being beneficial to increasing the specific discharge capacity.
Disclosure of Invention
The invention aims to avoid the defects of the prior art and provides an indium-doped zinc oxide composite reduced graphene oxide zinc-nickel secondary battery cathode material and a preparation method thereof. By using a hydrothermal method, indium atoms with atomic radius close to that of zinc atoms are doped into zinc oxide crystal lattices to replace the positions of partial zinc elements, and the number of free electrons in a zinc oxide matrix is increased to increase the carrier concentration, so that the conductivity of the material is enhanced; through the interaction between the metal zinc and the oxygen-containing functional groups on the surface of the graphite oxide, the zinc oxide is supported on the surface of the reduced graphene oxide, the conductivity of the material is further enhanced, and the reduced graphene oxide can inhibit the dissolution of the zinc oxide in electrolyte, so that the dendritic growth and electrode deformation of a zinc cathode are inhibited, and finally, the zinc-nickel secondary battery cathode material with high specific capacity and long cycle life is obtained.
An indium-doped zinc oxide composite reduced graphene oxide material is characterized in that: the zinc oxide is wurtzite zinc oxide; substituting indium for part of zinc positions in the zinc oxide crystal lattice by a hydrothermal synthesis method; and supporting the indium-doped zinc oxide on a graphene sheet layer.
The atomic ratio of the indium element to the zinc element is 0.01: 1-0.1: 1; the mass of the reduced graphene oxide accounts for 2-25% of the total mass of the composite material.
By controlling the time of the hydrothermal reaction, the particle size of the indium-doped zinc oxide in the synthesized indium-doped zinc oxide composite graphene oxide material is about 10-20 nanometers, and the indium-doped zinc oxide composite graphene oxide material is supported on the sheet-like reduced graphene oxide sheet with the area of about several hundred nanometers. The structure has a large specific surface area, and is beneficial to full contact between an active substance and electrolyte, so that electrode polarization can be reduced; meanwhile, the reduced graphene oxide can inhibit zinc oxide from being dissolved in the electrolyte, so that dendritic crystal growth and electrode deformation can be reduced, and the cycle life of the battery can be prolonged.
The indium-doped zinc oxide composite reduced graphene oxide material is characterized in that the thickness of the composite reduced graphene oxide material is 4-5 nanometers.
The preparation method of the indium-doped zinc oxide composite reduced graphene oxide material is characterized in that the hydrothermal reaction time is controlled, the doping amount of indium element and the using amount of composite reduced graphene oxide are controlled, and the preparation method specifically comprises the following steps:
step one, preparing an indium-doped zinc oxide composite reduced graphene oxide material
Dissolving zinc acetate and indium chloride in deionized water, simultaneously adding urea and potassium citrate, uniformly stirring, adding graphite oxide, stirring for a period of time, and carrying out ultrasonic treatment on reactants for a plurality of minutes. The resulting mixture was then transferred to a reaction kettle and reacted at a temperature and for a period of time. And after the reaction kettle is cooled to room temperature, centrifugally washing the reaction kettle for more than 3 times by using deionized water, and then drying the reaction kettle by using a vacuum drying oven to finally obtain the indium-doped zinc oxide composite reduced graphene oxide material.
The mass ratio of the zinc acetate to the indium chloride is 1: 0.01-1: 0.1; the mass ratio of the zinc acetate to the urea is 1: 1-1: 3; the mass ratio of the zinc acetate to the potassium citrate is 1: 0.1-1: 0.2; the mass ratio of the zinc acetate to the graphite oxide is 1: 0.02-1: 0.2; the concentration of the zinc acetate in the deionized water is 5 mg/mL-20 mg/mL.
The ultrasonic treatment time is 5-15 Min; the hydrothermal reaction temperature is 100-150 ℃, and the reaction time is 8-15 h;
the vacuum drying temperature is 60-80 ℃, and the drying time is 8-12 h.
The cathode electrode material of the zinc-nickel secondary battery comprises the following components in percentage by mass: 1: 1-7: 1.5:1.5 indium-doped zinc oxide composite reduced graphene oxide material, conductive carbon black and a binder polyvinylidene fluoride.
Step two, preparing the cathode of the zinc-nickel secondary battery
Weighing a certain amount of prepared indium-doped zinc oxide composite reduced graphene oxide material, mixing the indium-doped zinc oxide composite reduced graphene oxide material with conductive carbon black and polyvinylidene fluoride according to the mass ratio of 8:1:1, fully grinding, dropwise adding a proper amount of N-methyl-2-pyrrolidone into a dropper, fully stirring, coating the uniformly mixed electrode material on a tin-plated copper mesh, and drying for 4-6 hours at the temperature of 60-80 ℃ by using a forced air drying oven. Mixing commercial trivalent cobalt-coated spherical nickel, nickel powder and polytetrafluoroethylene according to a ratio of 85:10:5, dropwise adding a small amount of water, uniformly stirring, coating the mixture on foamed nickel, and drying the foamed nickel for 4-6 hours at 60-80 ℃ by using a blast drying oven to serve as a counter electrode, wherein the theoretical capacity of the electrode is more than 3 times of that of a negative electrode. And (3) a polypropylene microporous membrane is used as a diaphragm, and a 6mol/L saturated ZnO KOH solution is used as an electrolyte to assemble the soft package battery. And then, carrying out electrochemical performance test on the prepared battery in a voltage range of 1.2-1.9V by using a LAND-CT2001A battery test system.
Test results show that the indium-doped zinc oxide composite reduced graphene oxide material obtained by the invention has excellent discharge performance and long cycle life. When the zinc-nickel composite material is used as a negative electrode active material of a zinc-nickel secondary battery, the specific discharge capacity of the zinc-nickel composite material still reaches 570.4mAh g after 100 charge-discharge cycles under the current density of 0.5C-1。
The characteristics of the indium-doped zinc oxide composite reduced graphene oxide material are shown as follows: indium-doped zinc oxide particles with the particle size of about 10-20 nanometers are supported on a reduced graphene oxide sheet layer with the area of about several hundred nanometers; the thickness of the reduced graphene oxide layer is 4-5 nanometers; the atomic ratio of the indium element to the manganese element is 0.01: 1-0.1: 1; has larger specific surface area and long cycle life.
Compared with the prior art, the invention has the beneficial effects that:
(1) the raw materials adopted by the invention are zinc acetate, urea, potassium citrate, a small amount of graphite oxide and a small amount of indium chloride, and the material has wide sources, is green and safe and has low price.
(2) The hydrothermal method is simple, the preparation conditions are easy to control, and large-scale production can be realized.
(3) The electrode material obtained by the method has high discharge specific capacity and long cycle life.
Drawings
Fig. 1 is a transmission electron microscope image of a 3% indium-doped zinc oxide composite reduced graphene oxide (50mg) material.
Fig. 2 is an XRD picture of 3% indium-doped zinc oxide composite reduced graphene oxide (50mg) material.
Fig. 3 is a discharge curve of 3% indium-doped zinc oxide composite reduced graphene oxide (50mg) material at a current density of 0.5C.
Fig. 4 is a discharge curve of a 6% indium-doped zinc oxide composite reduced graphene oxide (50mg) material at a current density of 0.5C.
Fig. 5 is a discharge curve of 3% indium-doped zinc oxide composite reduced graphene oxide (30mg) material at a current density of 0.5C.
Fig. 6 is a discharge curve of 3% indium doped zinc oxide and zinc oxide at a current density of 0.5C.
Detailed Description
The invention will be described in further detail below with reference to the drawings and examples.
The invention relates to a preparation method of an indium-doped zinc oxide composite reduced graphene oxide zinc-nickel secondary battery cathode material, which comprises the following steps:
step one, preparing an indium-doped zinc oxide composite reduced graphene oxide material
Dissolving zinc acetate and indium chloride in deionized water, simultaneously adding urea and potassium citrate, uniformly stirring, adding graphite oxide, stirring for a period of time, and carrying out ultrasonic treatment on reactants for a plurality of minutes. The resulting mixture was then transferred to a reaction kettle and reacted at a temperature and for a period of time. And after the reaction kettle is cooled to room temperature, centrifugally washing the reaction kettle for more than 3 times by using deionized water, and then drying the reaction kettle by using a vacuum drying oven to finally obtain the indium-doped zinc oxide composite reduced graphene oxide material.
The mass ratio of the zinc acetate to the indium chloride is 1: 0.01-1: 0.1; the mass ratio of the zinc acetate to the urea is 1: 1-1: 3; the mass ratio of the zinc acetate to the potassium citrate is 1: 0.1-1: 0.2; the mass ratio of the zinc acetate to the graphite oxide is 1: 0.02-1: 0.2; the concentration of the zinc acetate in the deionized water is 5 mg/mL-20 mg/mL.
The ultrasonic treatment time is 5-15 Min; the hydrothermal reaction temperature is 100-150 ℃, and the reaction time is 8-15 h;
the vacuum drying temperature is 60-80 ℃, and the drying time is 8-12 h.
Step two, preparing the cathode of the zinc-nickel secondary battery
Weighing a certain amount of the obtained indium-doped zinc oxide composite reduced graphene oxide material, mixing the indium-doped zinc oxide composite reduced graphene oxide material with conductive carbon black and a binding agent polyvinylidene fluoride according to a mass ratio of 8:1:1, fully grinding, dropwise adding a proper amount of N-methyl-2-pyrrolidone by using a dropper, fully stirring, coating the uniformly mixed electrode material on a tin-plated copper mesh, and drying for 4-6 hours at 60-80 ℃ by using a blast drying oven. Mixing commercial trivalent cobalt-coated spherical nickel, nickel powder and polytetrafluoroethylene according to a ratio of 85:10:5, dropwise adding a small amount of water, uniformly stirring, coating the mixture on foamed nickel, drying for 4-6 hours at 60-80 ℃ by using a blast drying oven, and then using the dried product as a counter electrode, wherein the theoretical capacity of the electrode is more than 3 times of that of a negative electrode. And (3) a polypropylene microporous membrane is used as a diaphragm, and a 6mol/L saturated ZnO KOH solution is used as an electrolyte to assemble the soft package battery. And then, carrying out electrochemical performance test on the prepared battery in a voltage range of 1.2-1.9V by using a LAND-CT2001A battery test system.
Example 1
Step one, preparing an indium-doped zinc oxide composite reduced graphene oxide material
1.3170g of zinc acetate and 0.0395g of indium chloride are dissolved in deionized water, 2.8818g of urea and 0.1838g of potassium citrate are added at the same time, after the mixture is stirred for a plurality of minutes until the mixture is uniform, 0.0500g of graphene oxide is added, after the mixture is stirred for a period of time, the reactant is subjected to ultrasonic treatment for 10Min, then the obtained solution is transferred to a reaction kettle, and the reaction is carried out for a period of 12 hours at a certain temperature of 120 ℃. And after the reaction kettle is cooled to room temperature, centrifugally washing the reaction kettle for more than 3 times by using deionized water, and drying the reaction kettle for 10 hours at the temperature of 60 ℃ by using a vacuum drying oven to obtain the indium-doped zinc oxide composite reduced graphene oxide material.
Step two, preparing the cathode of the zinc-nickel secondary battery
Weighing 80mg of the obtained indium-doped zinc oxide composite reduced graphene oxide material, mixing the indium-doped zinc oxide composite reduced graphene oxide material with conductive carbon black and a binding agent polyvinylidene fluoride according to a mass ratio of 8:1:1, fully grinding, dripping 3-5 drops of N-methyl-2-pyrrolidone by using a dropper, fully stirring, coating the uniformly mixed electrode material on a tin-plated copper mesh, and drying for 6 hours at 80 ℃ by using a blast drying oven. Mixing commercial trivalent cobalt-coated spherical nickel, nickel powder and polytetrafluoroethylene according to a ratio of 85:10:5, dripping a small amount of water, uniformly stirring, coating the mixture on foamed nickel, drying for 6 hours at 80 ℃ by using a blast drying oven, and then using the dried product as a counter electrode, wherein the theoretical capacity of the electrode is more than 3 times of that of a negative electrode. And (3) a polypropylene microporous membrane is used as a diaphragm, and a 6mol/L saturated ZnO KOH solution is used as an electrolyte to assemble the soft package battery. And then, carrying out electrochemical performance test on the prepared battery in a voltage range of 1.2-1.9V by using a LAND-CT2001A battery test system.
Fig. 1 is a transmission electron micrograph of the synthesized indium-doped zinc oxide composite reduced graphene oxide material, and it can be seen that the material has a lamellar structure, and indium-doped particles with a particle size of about 10-20 nm are supported on a reduced graphene oxide lamellar layer with an area of about several hundred nm.
Fig. 2 is an XRD picture of the synthesized indium-doped zinc oxide composite reduced graphene oxide material. The figure shows samples, which have typical characteristic peaks (100), (002), (101), (102), (110), (103), (112) and the like of zinc oxide, and the synthesized samples are proved to be wurtzite zinc oxide; and no characteristic peak of indium oxide appears, which proves that the indium element is doped into the zinc oxide crystal lattice.
FIG. 3 is a graph of the discharge of the prepared material at a current density of 0.5C. It is obvious from the figure that the prepared material has good cycling stability, and the specific discharge capacity of the material can still be maintained at 589.7mAh g after 100 times of charge-discharge cycles-1。
Example 2
Step one, preparing an indium-doped zinc oxide composite reduced graphene oxide material
1.3170g of zinc acetate and 0.0790g of indium chloride are dissolved in deionized water, 2.8818g of urea and 0.1838g of potassium citrate are added at the same time, after the mixture is stirred for a plurality of minutes until the mixture is uniform, 0.0500g of graphene oxide is added, after the mixture is stirred for a period of time, the reactant is subjected to ultrasonic treatment for 10Min, then the obtained solution is transferred to a reaction kettle, and the reaction is carried out for a period of 12 hours at a certain temperature of 120 ℃. And after the reaction kettle is cooled to room temperature, centrifugally washing the reaction kettle for more than 3 times by using deionized water, and drying the reaction kettle for 10 hours at the temperature of 60 ℃ by using a vacuum drying oven to obtain the indium-doped zinc oxide composite reduced graphene oxide material.
Step two, preparing the cathode of the zinc-nickel secondary battery
Weighing 80mg of the obtained indium-doped zinc oxide composite reduced graphene oxide material, mixing the indium-doped zinc oxide composite reduced graphene oxide material with conductive carbon black and a binding agent polyvinylidene fluoride according to a mass ratio of 8:1:1, fully grinding, dripping 3-5 drops of N-methyl-2-pyrrolidone by using a dropper, fully stirring, coating the uniformly mixed electrode material on a tin-plated copper mesh, and drying for 6 hours at 80 ℃ by using a blast drying oven. Mixing commercial trivalent cobalt-coated spherical nickel, nickel powder and polytetrafluoroethylene according to a ratio of 85:10:5, dripping a small amount of water, uniformly stirring, coating the mixture on foamed nickel, drying for 6 hours at 80 ℃ by using a blast drying oven, and then using the dried product as a counter electrode, wherein the theoretical capacity of the electrode is more than 3 times of that of a negative electrode. And (3) a polypropylene microporous membrane is used as a diaphragm, and a 6mol/L saturated ZnO KOH solution is used as an electrolyte to assemble the soft package battery. And then, carrying out electrochemical performance test on the prepared battery in a voltage range of 1.2-1.9V by using a LAND-CT2001A battery test system.
The method of the present invention was substantially the same as that used in example 1 except that the indium doping amount was increased to 6%. The discharge curve of the electrode material at a current density of 0.5C with the material prepared in example 1 is shown in fig. 4, from which it can be seen that the specific discharge capacity of the material prepared by the method used in this example is lower than that of example 1 at the same current density. This is because too much indium doping affects the amount of zinc oxide produced and the conductivity, and thus the electrochemical performance. By comparison, 3% is a better indium doping ratio.
Example 3
Step one, preparing an indium-doped zinc oxide composite reduced graphene oxide material
1.3170g of zinc acetate and 0.0395g of indium chloride are dissolved in deionized water, 2.8818g of urea and 0.1838g of potassium citrate are added at the same time, after the mixture is stirred for a plurality of minutes until the mixture is uniform, 0.0300g of graphene oxide is added, after the mixture is stirred for a period of time, the reactant is subjected to ultrasonic treatment for 10Min, then the obtained solution is transferred to a reaction kettle, and the reaction is carried out for a period of 12 hours at a certain temperature of 120 ℃. And after the reaction kettle is cooled to room temperature, centrifugally washing the reaction kettle for more than 3 times by using deionized water, and drying the reaction kettle for 10 hours at the temperature of 60 ℃ by using a vacuum drying oven to obtain the indium-doped zinc oxide composite reduced graphene oxide material.
Step two, preparing the cathode of the zinc-nickel secondary battery
Weighing 80mg of the obtained indium-doped zinc oxide composite reduced graphene oxide material, mixing the indium-doped zinc oxide composite reduced graphene oxide material with conductive carbon black and a binding agent polyvinylidene fluoride according to a mass ratio of 8:1:1, fully grinding, dripping 3-5 drops of N-methyl-2-pyrrolidone by using a dropper, fully stirring, coating the uniformly mixed electrode material on a tin-plated copper mesh, and drying for 6 hours at 80 ℃ by using a blast drying oven. Mixing commercial trivalent cobalt-coated spherical nickel, nickel powder and polytetrafluoroethylene according to a ratio of 85:10:5, dripping a small amount of water, uniformly stirring, coating the mixture on foamed nickel, drying for 6 hours at 80 ℃ by using a blast drying oven, and then using the dried product as a counter electrode, wherein the theoretical capacity of the electrode is more than 3 times of that of a negative electrode. And (3) a polypropylene microporous membrane is used as a diaphragm, and a 6mol/L saturated ZnO KOH solution is used as an electrolyte to assemble the soft package battery. And then, carrying out electrochemical performance test on the prepared battery in a voltage range of 1.2-1.9V by using a LAND-CT2001A battery test system.
The invention is essentially the same as that used in example 1, except that the amount of graphite oxide used is reduced to 30 mg. The discharge curve of the electrode material at a current density of 0.5C with the material prepared in example 1 is shown in fig. 5, and it can be seen that the specific discharge capacity of the material prepared by the method used in this example is lower than that of example 1 at the same current density. This is because the amount of reduced graphene oxide in the synthesized composite material affects the conductivity of the synthesized material and the dissolution of zinc oxide in the electrolyte, which in turn affects its performance.
Comparative example 1
Step one, preparing zinc oxide material
1.3170g of zinc acetate is dissolved in deionized water, 2.8818g of urea and 0.1838g of potassium citrate are added at the same time, ultrasonic treatment is carried out for 10Min after the mixture is stirred for a plurality of minutes to be uniform, and then the obtained solution is transferred into a reaction kettle and reacts for a period of 12 hours at a certain temperature of 120 ℃. And after the reaction kettle is cooled to room temperature, centrifugally washing the reaction kettle for more than 3 times by using deionized water, and drying the reaction kettle for 10 hours at the temperature of 60 ℃ by using a vacuum drying oven to obtain the zinc oxide material.
Step two, preparing the cathode of the zinc-nickel secondary battery
Weighing 80mg of the obtained zinc oxide material, mixing the zinc oxide material with conductive carbon black and a binding agent polyvinylidene fluoride according to a mass ratio of 8:1:1, fully grinding, dripping 3-5 drops of N-methyl-2-pyrrolidone by a dropper, fully stirring, coating the uniformly mixed electrode material on a tinned copper mesh, and drying for 6 hours at 80 ℃ by using a blast drying oven. Mixing commercial trivalent cobalt-coated spherical nickel, nickel powder and polytetrafluoroethylene according to a ratio of 85:10:5, dripping a small amount of water, uniformly stirring, coating the mixture on foamed nickel, drying for 6 hours at 80 ℃ by using a blast drying oven, and then using the dried product as a counter electrode, wherein the theoretical capacity of the electrode is more than 3 times of that of a negative electrode. And (3) a polypropylene microporous membrane is used as a diaphragm, and a 6mol/L saturated ZnO KOH solution is used as an electrolyte to assemble the soft package battery. And then, carrying out electrochemical performance test on the prepared battery in a voltage range of 1.2-1.9V by using a LAND-CT2001A battery test system.
The method of the present invention is substantially the same as that used in example 1, except that indium doping is not performed and recombination with reduced graphene oxide is not performed. The discharge curve of the electrode material at a current density of 0.5C with the material prepared in example 1 is shown in fig. 6, and it can be seen that the specific discharge capacity of the material prepared by the method used in this comparative example is much lower than that of example 1 at the same current density. This is because indium doping and reduced graphene oxide recombination affect the conductivity of the zinc oxide material and inhibit the dissolution of zinc oxide. By comparison, the material obtained by compounding iron doping and reduced graphene oxide has better performance.
Comparative example 2
Step one, preparing indium-doped zinc oxide material
1.3170g of zinc acetate and 0.0395g of indium chloride are dissolved in deionized water, 2.8818g of urea and 0.1838g of potassium citrate are added at the same time, the mixture is stirred for a plurality of minutes until uniform and then is subjected to ultrasonic treatment for 10Min, and then the obtained solution is transferred to a reaction kettle and is reacted for a period of 12 hours at a certain temperature of 120 ℃. And after the reaction kettle is cooled to room temperature, centrifugally washing the reaction kettle for more than 3 times by using deionized water, and drying the reaction kettle for 10 hours at the temperature of 60 ℃ by using a vacuum drying oven to obtain the indium-doped zinc oxide material.
Step two, preparing the cathode of the zinc-nickel secondary battery
Weighing 80mg of the obtained indium-doped zinc oxide material, mixing the indium-doped zinc oxide material with conductive carbon black and a binding agent polyvinylidene fluoride according to the mass ratio of 8:1:1, fully grinding, dropwise adding 3-5 drops of N-methyl-2-pyrrolidone by a dropper, fully stirring, coating the uniformly mixed electrode material on a tin-plated copper mesh, and drying for 6 hours at 80 ℃ by using a blast drying oven. Mixing commercial trivalent cobalt-coated spherical nickel, nickel powder and polytetrafluoroethylene according to a ratio of 85:10:5, dripping a small amount of water, uniformly stirring, coating the mixture on foamed nickel, drying for 6 hours at 80 ℃ by using a blast drying oven, and then using the dried product as a counter electrode, wherein the theoretical capacity of the electrode is more than 3 times of that of a negative electrode. And (3) a polypropylene microporous membrane is used as a diaphragm, and a 6mol/L saturated ZnO KOH solution is used as an electrolyte to assemble the soft package battery. And then, carrying out electrochemical performance test on the prepared battery in a voltage range of 1.2-1.9V by using a LAND-CT2001A battery test system.
The method of the present invention is substantially the same as that used in example 1, except that no recombination with reduced graphene oxide is performed. The discharge curve of the electrode material at a current density of 0.5C with the material prepared in example 1 is shown in fig. 6, and it can be seen that the specific discharge capacity of the material prepared by the method used in this comparative example is much lower than that of example 1 at the same current density. This is because the reduced graphene oxide recombination affects the conductivity of the zinc oxide material and inhibits the dissolution of zinc oxide. Through comparison, the material obtained by compounding the reduced graphene oxide has better performance.
Comparative example 3
Step one, preparing an indium-doped zinc oxide composite reduced graphene oxide material
1.3170g of zinc acetate and 0.0133g of indium chloride are dissolved in deionized water, 2.8818g of urea and 0.1838g of potassium citrate are added simultaneously, after stirring for a plurality of minutes until the mixture is uniform, 0.0500g of graphene oxide is added, after stirring for a period of time, the reactant is subjected to ultrasonic treatment for 10Min, then the obtained solution is transferred to a reaction kettle and reacts for a period of 12 hours at a certain temperature of 120 ℃. And after the reaction kettle is cooled to room temperature, centrifugally washing the reaction kettle for more than 3 times by using deionized water, and drying the reaction kettle for 10 hours at the temperature of 60 ℃ by using a vacuum drying oven to obtain the indium-doped zinc oxide composite reduced graphene oxide material.
Step two, preparing the cathode of the zinc-nickel secondary battery
Weighing 80mg of the obtained indium-doped zinc oxide composite reduced graphene oxide material, mixing the indium-doped zinc oxide composite reduced graphene oxide material with conductive carbon black and a binding agent polyvinylidene fluoride according to a mass ratio of 8:1:1, fully grinding, dripping 3-5 drops of N-methyl-2-pyrrolidone by using a dropper, fully stirring, coating the uniformly mixed electrode material on a tin-plated copper mesh, and drying for 6 hours at 80 ℃ by using a blast drying oven. Mixing commercial trivalent cobalt-coated spherical nickel, nickel powder and polytetrafluoroethylene according to a ratio of 85:10:5, dripping a small amount of water, uniformly stirring, coating the mixture on foamed nickel, drying for 6 hours at 80 ℃ by using a blast drying oven, and then using the dried product as a counter electrode, wherein the theoretical capacity of the electrode is more than 3 times of that of a negative electrode. And (3) a polypropylene microporous membrane is used as a diaphragm, and a 6mol/L saturated ZnO KOH solution is used as an electrolyte to assemble the soft package battery. And then, carrying out electrochemical performance test on the prepared battery in a voltage range of 1.2-1.9V by using a LAND-CT2001A battery test system.
The method of the present invention was substantially the same as that used in example 1 except that the indium doping amount was reduced to 1%. Compared with the material prepared in the example 1, the material prepared by the method in the example has lower specific discharge capacity than the material prepared in the example 1 under the same current density. This is because too small amount of indium incorporation limits the improvement of the conductivity of zinc oxide, and affects the electrochemical properties thereof.
Comparative example 4
Step one, preparing an indium-doped zinc oxide composite reduced graphene oxide material
1.3170g of zinc acetate and 0.0395g of indium chloride are dissolved in deionized water, 2.8818g of urea and 0.1838g of potassium citrate are added at the same time, after stirring for a few minutes until the mixture is uniform, 0.1000g of graphene oxide is added, after stirring for a period of time, the reactant is subjected to ultrasonic treatment for 10Min, then the obtained solution is transferred to a reaction kettle, and the reaction is carried out for a period of 12 hours at a certain temperature of 120 ℃. And after the reaction kettle is cooled to room temperature, centrifugally washing the reaction kettle for more than 3 times by using deionized water, and drying the reaction kettle for 10 hours at the temperature of 60 ℃ by using a vacuum drying oven to obtain the indium-doped zinc oxide composite reduced graphene oxide material.
Step two, preparing the cathode of the zinc-nickel secondary battery
Weighing 80mg of the obtained indium-doped zinc oxide composite reduced graphene oxide material, mixing the indium-doped zinc oxide composite reduced graphene oxide material with conductive carbon black and a binding agent polyvinylidene fluoride according to a mass ratio of 8:1:1, fully grinding, dripping 3-5 drops of N-methyl-2-pyrrolidone by using a dropper, fully stirring, coating the uniformly mixed electrode material on a tin-plated copper mesh, and drying for 6 hours at 80 ℃ by using a blast drying oven. Mixing commercial trivalent cobalt-coated spherical nickel, nickel powder and polytetrafluoroethylene according to a ratio of 85:10:5, dripping a small amount of water, uniformly stirring, coating the mixture on foamed nickel, drying for 6 hours at 80 ℃ by using a blast drying oven, and then using the dried product as a counter electrode, wherein the theoretical capacity of the electrode is more than 3 times of that of a negative electrode. And (3) a polypropylene microporous membrane is used as a diaphragm, and a 6mol/L saturated ZnO KOH solution is used as an electrolyte to assemble the soft package battery. And then, carrying out electrochemical performance test on the prepared battery in a voltage range of 1.2-1.9V by using a LAND-CT2001A battery test system.
The invention is essentially the same as that employed in example 1 except that the amount of graphite oxide used is increased to 0.1000 g. The specific discharge capacity of the electrode material prepared by the method is lower than that of the electrode material prepared in example 1 under the same current density. This is because the excessive carbon content causes the increase of hydrogen evolution in the negative electrode, and the performance of the electrode is deteriorated.
Comparative example 5
Step one, preparing an indium-doped zinc oxide composite reduced graphene oxide material
1.3170g of zinc acetate and 0.0395g of indium chloride are dissolved in deionized water, 2.8818g of urea and 0.1838g of potassium citrate are added at the same time, after the mixture is stirred for a plurality of minutes until the mixture is uniform, 0.0500g of graphene oxide is added, after the mixture is stirred for a period of time, the reactant is subjected to ultrasonic treatment for 10Min, and then the obtained solution is transferred to a reaction kettle and reacts for 8 hours at a certain temperature of 120 ℃. And after the reaction kettle is cooled to room temperature, centrifugally washing the reaction kettle for more than 3 times by using deionized water, and drying the reaction kettle for 10 hours at the temperature of 60 ℃ by using a vacuum drying oven to obtain the indium-doped zinc oxide composite reduced graphene oxide material.
Step two, preparing the cathode of the zinc-nickel secondary battery
Weighing 80mg of the obtained indium-doped zinc oxide composite reduced graphene oxide material, mixing the indium-doped zinc oxide composite reduced graphene oxide material with conductive carbon black and a binding agent polyvinylidene fluoride according to a mass ratio of 8:1:1, fully grinding, dripping 3-5 drops of N-methyl-2-pyrrolidone by using a dropper, fully stirring, coating the uniformly mixed electrode material on a tin-plated copper mesh, and drying for 6 hours at 80 ℃ by using a blast drying oven. Mixing commercial trivalent cobalt-coated spherical nickel, nickel powder and polytetrafluoroethylene according to a ratio of 85:10:5, dripping a small amount of water, uniformly stirring, coating the mixture on foamed nickel, drying for 6 hours at 80 ℃ by using a blast drying oven, and then using the dried product as a counter electrode, wherein the theoretical capacity of the electrode is more than 3 times of that of a negative electrode. And (3) a polypropylene microporous membrane is used as a diaphragm, and a 6mol/L saturated ZnO KOH solution is used as an electrolyte to assemble the soft package battery. And then, carrying out electrochemical performance test on the prepared battery in a voltage range of 1.2-1.9V by using a LAND-CT2001A battery test system.
The present invention was substantially the same as that employed in example 1 except that the hydrothermal reaction time was shortened. The specific discharge capacity of the electrode material prepared by the method is lower than that of the electrode material prepared in example 1 under the same current density. This is because the hydrothermal reaction time affects the crystallinity and particle size of the manganese oxide to be synthesized, and too short a reaction time deteriorates the crystallinity and affects the performance.
Comparative example 6
Step one, preparing an indium-doped zinc oxide composite reduced graphene oxide material
1.3170g of zinc acetate and 0.0395g of indium chloride are dissolved in deionized water, 2.8818g of urea and 0.1838g of potassium citrate are added at the same time, after the mixture is stirred for a plurality of minutes until the mixture is uniform, 0.0500g of graphene oxide is added, after the mixture is stirred for a period of time, the reactant is subjected to ultrasonic treatment for 10Min, and then the obtained solution is transferred to a reaction kettle and reacts for 15 hours at a certain temperature of 120 ℃. And after the reaction kettle is cooled to room temperature, centrifugally washing the reaction kettle for more than 3 times by using deionized water, and drying the reaction kettle for 10 hours at the temperature of 60 ℃ by using a vacuum drying oven to obtain the indium-doped zinc oxide composite reduced graphene oxide material.
Step two, preparing the cathode of the zinc-nickel secondary battery
Weighing 80mg of the obtained indium-doped zinc oxide composite reduced graphene oxide material, mixing the indium-doped zinc oxide composite reduced graphene oxide material with conductive carbon black and a binding agent polyvinylidene fluoride according to a mass ratio of 8:1:1, fully grinding, dripping 3-5 drops of N-methyl-2-pyrrolidone by using a dropper, fully stirring, coating the uniformly mixed electrode material on a tin-plated copper mesh, and drying for 6 hours at 80 ℃ by using a blast drying oven. Mixing commercial trivalent cobalt-coated spherical nickel, nickel powder and polytetrafluoroethylene according to a ratio of 85:10:5, dripping a small amount of water, uniformly stirring, coating the mixture on foamed nickel, drying for 6 hours at 80 ℃ by using a blast drying oven, and then using the dried product as a counter electrode, wherein the theoretical capacity of the electrode is more than 3 times of that of a negative electrode. And (3) a polypropylene microporous membrane is used as a diaphragm, and a 6mol/L saturated ZnO KOH solution is used as an electrolyte to assemble the soft package battery. And then, carrying out electrochemical performance test on the prepared battery in a voltage range of 1.2-1.9V by using a LAND-CT2001A battery test system.
The present invention was substantially the same as that employed in example 1 except that the hydrothermal reaction time was increased. The specific discharge capacity of the electrode material and the material prepared in the example 1 is lower than that of the material prepared in the example 1 under the same current density. This is because the hydrothermal reaction time affects the particle size of the synthesized zinc oxide, and an excessively long reaction time increases the size of the particles, which in turn affects the performance thereof.
Comparative example 7
Step one, preparing indium-doped zinc oxide material
1.3170g of zinc acetate and 0.0395g of indium chloride are dissolved in deionized water, 2.8818g of urea and 0.1838g of potassium citrate are added simultaneously, the mixture is stirred for a plurality of minutes until the mixture is uniform, then the reactant is subjected to ultrasonic treatment for 10Min, and then the obtained solution is transferred to a reaction kettle and reacts for 15 hours at a certain temperature of 120 ℃. And after the reaction kettle is cooled to room temperature, centrifugally washing the reaction kettle for more than 3 times by using deionized water, and drying the reaction kettle for 10 hours at the temperature of 60 ℃ by using a vacuum drying oven to finally obtain the indium-doped zinc oxide material.
Step two, preparing the cathode of the zinc-nickel secondary battery
Weighing 80mg of the obtained indium-doped zinc oxide material, mixing the indium-doped zinc oxide material with conductive carbon black and a binding agent polyvinylidene fluoride according to the mass ratio of 8:1:1, fully grinding, physically mixing with 50mg of dry graphite oxide, dropwise adding 3-5 drops of N-methyl-2-pyrrolidone by a dropper, fully stirring, coating the uniformly mixed electrode material on a tinned copper mesh, and drying for 6 hours at 80 ℃ by using a blast drying oven. Mixing commercial trivalent cobalt-coated spherical nickel, nickel powder and polytetrafluoroethylene according to a ratio of 85:10:5, dripping a small amount of water, uniformly stirring, coating the mixture on foamed nickel, drying for 6 hours at 80 ℃ by using a blast drying oven, and then using the dried product as a counter electrode, wherein the theoretical capacity of the electrode is more than 3 times of that of a negative electrode. And (3) a polypropylene microporous membrane is used as a diaphragm, and a 6mol/L saturated ZnO KOH solution is used as an electrolyte to assemble the soft package battery. And then, carrying out electrochemical performance test on the prepared battery in a voltage range of 1.2-1.9V by using a LAND-CT2001A battery test system.
The method of the present invention is substantially the same as that used in example 1, except that indium-doped manganese oxide is physically mixed with reduced graphene oxide. The specific discharge capacity of the material prepared by the method of the comparative example is much lower than that of the material prepared by the example 1 under the same current density. The reason is that the graphene can inhibit the dissolution of zinc oxide in the electrolyte and further enhance the conductivity of the material, so that the specific discharge capacity is increased, the cycle life is prolonged, and the same effect is difficult to achieve by physical mixing.
Claims (8)
1. An indium-doped zinc oxide composite reduced graphene oxide material is characterized in that:
the zinc oxide is wurtzite zinc oxide; indium is substituted for the position of partial zinc in zinc oxide crystal lattices by a hydrothermal synthesis method to obtain indium-doped zinc oxide; and loading the indium-doped zinc oxide on the reduced graphene oxide sheet layer to obtain the indium-doped zinc oxide composite reduced graphene oxide material, namely the composite material.
2. The indium-doped zinc oxide composite reduced graphene oxide material according to claim 1, wherein: the atomic ratio of indium element to zinc element in the indium-doped zinc oxide is 0.01: 1-0.1: 1 (preferably 0.01: 1-0.05: 1); the mass of the reduced graphene oxide accounts for 2-25% (preferably 2-15%) of the total mass of the composite material.
3. The indium-doped zinc oxide composite reduced graphene oxide material according to claim 1, wherein: the particle size of the indium-doped zinc oxide in the composite material is 10-20 (preferably 10-15) nanometers, and the indium-doped zinc oxide is supported on a sheet-like reduced graphene oxide sheet with the area of 100-800 square nanometers (preferably 200-500 square nanometers).
4. The indium-doped zinc oxide composite reduced graphene oxide material according to claim 1, wherein: the thickness of the reduced graphene oxide is 4-5 nanometers.
5. A preparation method of the indium-doped zinc oxide composite reduced graphene oxide material as claimed in any one of claims 1 to 4, which is characterized by comprising the following steps:
preparing indium-doped zinc oxide;
dissolving zinc acetate and indium chloride in water, simultaneously adding urea and potassium citrate, stirring uniformly, adding graphite oxide, stirring uniformly, carrying out ultrasonic treatment on the mixture, transferring the obtained solution into a reaction kettle, and carrying out hydrothermal reaction for a period of time at a certain reaction temperature; after the reaction kettle is cooled to room temperature, centrifugally washing the reaction kettle for more than 3 times by using deionized water, and then drying the reaction kettle by using a vacuum drying oven to finally obtain the indium-doped zinc oxide composite reduced graphene oxide material;
the mass ratio of the zinc acetate to the indium chloride is 1: 0.01-1: 0.1; the mass ratio of the zinc acetate to the urea is 1: 1-1: 3; the mass ratio of the zinc acetate to the potassium citrate is 1: 0.1-1: 0.2; the mass ratio of the zinc acetate to the graphite oxide is 1: 0.01-1: 0.2; the concentration of the zinc acetate in the deionized water is 5 mg/mL-20 mg/mL;
the ultrasonic treatment time is 5-15 Min; the hydrothermal reaction temperature is 100-150 ℃, and the reaction time is 8-15 h.
6. The method of claim 5, wherein:
the vacuum drying temperature is 60-80 ℃, and the drying time is 8-12 h.
7. An application of the indium-doped zinc oxide composite reduced graphene oxide material as defined in any one of claims 1 to 4 as a negative electrode active material in a zinc-nickel secondary battery negative electrode.
8. Use according to claim 7, characterized in that:
the cathode electrode material of the zinc-nickel secondary battery comprises the following components in percentage by mass: 1: 1-7: 1.5:1.5 indium-doped zinc oxide composite reduced graphene oxide material, conductive carbon black and a binder polyvinylidene fluoride.
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