CN114551859A - Manganese-doped nickel hydroxide composite reduced graphene oxide material, preparation and application - Google Patents

Manganese-doped nickel hydroxide composite reduced graphene oxide material, preparation and application Download PDF

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CN114551859A
CN114551859A CN202011344870.2A CN202011344870A CN114551859A CN 114551859 A CN114551859 A CN 114551859A CN 202011344870 A CN202011344870 A CN 202011344870A CN 114551859 A CN114551859 A CN 114551859A
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manganese
nickel hydroxide
graphene oxide
reduced graphene
nickel
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王二东
张强
孙公权
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Dalian Institute of Chemical Physics of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/24—Alkaline accumulators
    • H01M10/30—Nickel accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract

The invention belongs to the field of inorganic chemical nano materials and related electrochemical technologies, and relates to a preparation method of a manganese-doped nickel hydroxide composite reduced graphene oxide material and a general method for applying the manganese-doped nickel hydroxide composite reduced graphene oxide material to a cathode of a zinc-nickel secondary battery. Manganese element is doped into a nickel hydroxide crystal lattice to replace the position of partial nickel element by using a hydrothermal synthesis method; and then coating reduced graphene oxide on the surface of the manganese-doped nickel hydroxide nanosheet. The conductivity of the nickel hydroxide material can be enhanced by doping manganese and coating reduced graphene oxide, and finally the positive electrode material of the zinc-nickel secondary battery with high specific capacity and long cycle life is obtained. The resulting composite material had a nano-platelet structure and exhibited extraordinary propertiesExcellent electrochemical performance. When the zinc-nickel alloy is used as a positive electrode material of a zinc-nickel secondary battery, the concentration is 105mg/cm2Under the condition of high loading capacity, the specific capacity of 224.6mAh/g and the specific capacity of 23.6mAh/cm are obtained under the current density of 0.1C2The specific discharge capacity of the lithium ion battery can still reach 165.6mAh g under the current density of 3C‑1。

Description

Manganese-doped nickel hydroxide composite reduced graphene oxide material, preparation and application
Technical Field
The invention relates to a preparation method of a manganese-doped nickel hydroxide composite reduced graphene oxide material and application of the material as a zinc-nickel secondary battery anode, 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 problems encountered in the research of the zinc-nickel secondary power supply are that the energy density of the battery is low, the price is relatively high and the like, and the main reasons are that the utilization rate of active substances is low due to poor conductivity of a nickel anode, and high surface capacity is difficult to realize; the use of a large amount of cobalt, which is expensive and toxic, results in high material price and affects the specific energy of the battery. Therefore, the research on the cathode material with good conductivity, high specific capacity and low price is the focus of the current zinc-nickel secondary battery. At present, the common methods for the modification research of the anode material of the zinc-nickel secondary battery comprise a cobalt element coating method, such as a method of coating the surface with cobalt oxide to enhance the conductivity of the material and further improve the specific discharge capacity of the material, but the method causes the material to be expensive and toxic; the crystal form control method is characterized in that alpha-nickel hydroxide with high theoretical capacity is synthesized to enable the material to have high specific capacity, but the alpha-nickel hydroxide is easy to generate crystal form transformation to cause poor battery cycle stability.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a manganese-doped nickel hydroxide composite reduced graphene oxide zinc-nickel secondary battery anode material based on a cobalt-free material design idea and a preparation method thereof. Manganese atoms with similar atomic radius to nickel atoms are doped into nickel hydroxide crystal lattices to replace the positions of partial manganese elements by using a hydrothermal synthesis method, so that the conductivity of the material is enhanced; the material is compounded with reduced graphene oxide to further enhance the conductivity of the material, and finally the zinc-nickel secondary battery anode material with good conductivity and high specific capacity is obtained.
The manganese-doped nickel hydroxide composite reduced graphene oxide material is characterized in that: the crystal form of the nickel hydroxide is beta type; substituting manganese for part of manganese in the nickel hydroxide crystal lattice by hydrothermal synthesis; and the reduced graphene oxide is coated on the surface of the material.
The atomic ratio of the manganese element to the nickel element is 0.01: 1-0.25: 1; the mass of the reduced graphene oxide accounts for 5-25% of the total mass of the composite material.
By controlling the time of the hydrothermal reaction, the concentration of the raw materials and the manganese doping amount, the synthesized manganese-doped nickel hydroxide composite reduced graphene oxide material is of a nanosheet structure, the particle size of the nanosheet is about 60-100 nanometers, and the redox graphene is coated on the surface of the material. 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 manganese doping and the reduced graphene oxide coating can enhance the conductivity of the material, so that the material has high specific capacity. The hydrothermal reaction time of less than 1 hour results in poor crystallization of the material, and the reaction time of more than 8 hours results in large particle size of the material. The concentration of the raw material is lower than the control concentration, so that the particle size of the material is reduced, and the tap density and the synthesis efficiency of the material are influenced; the concentration of the raw material is higher than the control concentration, which increases the particle size of the material and affects the discharge performance of the material. The composite amount of the manganese doping amount and the graphene is lower than the control amount, so that the conductivity of the material is deteriorated, and the discharge performance is reduced; the manganese doping amount and the graphene compounding amount are larger than the control amount, so that the proportion of active ingredients in the material is reduced, and the discharge performance is reduced.
The manganese-doped nickel hydroxide composite reduced graphene oxide material is characterized in that the thickness of the coated reduced graphene oxide is 5-8 nanometers.
The preparation method of the manganese-doped nickel hydroxide composite reduced graphene oxide material is characterized in that the hydrothermal reaction time is controlled, the doping amount of indium element and the concentration of used raw materials are controlled, and the preparation method comprises the following specific steps:
step one, preparing manganese-doped nickel hydroxide composite reduced graphene oxide material
Dissolving nickel sulfate and manganese sulfate in water, uniformly stirring, adding sodium hydroxide and ammonia water, uniformly stirring, adding graphite oxide, carrying out ultrasonic treatment on the mixture, transferring the obtained mixture into a reaction kettle, and carrying out hydrothermal reaction at a certain reaction temperature 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 manganese-doped nickel hydroxide composite reduced graphene oxide material.
The mass ratio of the nickel sulfate to the manganese sulfate is 1: 0.006-1: 0.215; the mass ratio of the nickel sulfate to the sodium hydroxide is 1: 0.3-1: 0.5; the mass ratio of the nickel sulfate to the ammonia water is 1: 0.05-1: 0.1; the mass ratio of the nickel sulfate to the graphite oxide is 1: 0.03-1: 0.1; the concentration of the nickel sulfate in water is 35 mg/mL-60 mg/mL;
the ultrasonic treatment time is 5-15 Min; the hydrothermal reaction temperature is 120-200 ℃, and the reaction time is 1-8 h. (ii) a
The vacuum drying temperature is 60-80 ℃, and the drying time is 8-12 h.
The positive electrode material of the zinc-nickel secondary battery comprises the following components in percentage by mass: 1: 1-7: 1.5:1.5 manganese-doped nickel hydroxide composite reduced graphene oxide, conductive carbon black and a binder polyvinylidene fluoride.
Step two, preparing the positive electrode of the zinc-nickel secondary battery
Weighing a certain amount of prepared manganese-doped nickel hydroxide composite reduced graphene oxide material, mixing the manganese-doped nickel hydroxide composite reduced graphene oxide material with conductive carbon black and polyvinylidene fluoride according to the mass ratio of 8:1: 1-7: 1.5:1.5, fully grinding, dropwise adding a proper amount of N-methyl-2-pyrrolidone into a dropper, fully stirring, coating the uniformly mixed electrode material on foamed nickel, and drying for 4-6 hours at the temperature of 60-80 ℃ by using a forced air drying oven. Mixing zinc oxide, zinc powder, bismuth trioxide and polytetrafluoroethylene according to the proportion of 80:12:3:5, dropwise adding a small amount of water, uniformly stirring, coating the mixture on a tin-plated copper net, drying for 4-6 hours at the temperature of 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 the positive electrode. 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 manganese-doped nickel hydroxide composite reduced graphene oxide material has excellent discharge performance. When used as the negative electrode active material of a zinc-nickel secondary battery, the content of the active material is 105mg/cm2Under the condition of high loading capacity and the current density of 0.1C, the specific discharge capacity of the lithium ion battery still reaches 224.6mAh g-1The specific discharge capacity of the material reaches 165.6mAh g when the surface capacity reaches 23.6mAh and the current density of 3C-1。
The manganese-doped nickel hydroxide composite reduced graphene oxide material is characterized in that: the surface of the manganese-doped nickel hydroxide nanosheet with the particle size of about 60-100 nanometers is coated with reduced graphene oxide; the thickness of the coated reduced graphene oxide is about 5-8 nanometers; the atomic ratio of the manganese element to the nickel element is 0.01: 1-0.25: 1; has larger specific surface area and excellent specific capacity.
Compared with the prior art, the invention has the beneficial effects that:
(1) the raw materials adopted by the invention are nickel sulfate, manganese sulfate, sodium hydroxide, ammonia water and a small amount of graphite oxide, and the material has wide sources, is green and safe and has low price.
(2) The conductivity of the nickel hydroxide material can be enhanced by adopting manganese doping and reduced graphene oxide coating.
(3) The hydrothermal method is simple, the preparation conditions are easy to control, and large-scale production can be realized.
(4) The electrode material obtained by the method has high specific discharge capacity.
According to the invention, the conductivity of the nickel hydroxide material can be enhanced by doping manganese and coating the reduced graphene oxide, so that the cathode material of the zinc-nickel secondary battery with high specific capacity and long cycle life is finally obtained. The resulting composite materialHas a nano sheet structure and simultaneously shows excellent electrochemical performance. When the zinc-nickel alloy is used as a positive electrode material of a zinc-nickel secondary battery, the concentration is 105mg/cm2Under the condition of high loading capacity, the specific capacity of 224.6mAh/g and the specific capacity of 23.6mAh/cm are obtained under the current density of 0.1C2The specific discharge capacity of the lithium ion battery can still reach 165.6mAh g under the current density of 3C-1. The excellent electrochemical performance shows that the zinc-nickel composite oxide has a very wide application prospect when being used as a positive electrode active material of a zinc-nickel secondary battery. Meanwhile, as the raw materials comprise nickel sulfate, manganese sulfate, sodium hydroxide, ammonia water, a small amount of graphite oxide and the like, the raw materials have wide sources and low prices, and the electrode material has simple and controllable preparation process and simple equipment, and is a method which is easy to carry out large-scale production.
Drawings
Fig. 1 is a scanning electron microscope picture of a 10 wt% redox graphene coated 10% (molar weight) manganese-doped nickel hydroxide material.
Fig. 2 is an XRD picture of 10 wt% redox graphene coated 10% (molar weight) manganese doped nickel hydroxide material.
FIG. 3 shows that the concentration of 10 wt% redox graphene coated 10% (by mol) manganese doped nickel hydroxide material is 105mg/cm2Specific discharge capacity and surface capacity under the condition of high loading capacity and current density of 0.1C and 3C.
Fig. 4 is a discharge curve of a 10 wt% redox graphene coated 6% (molar weight) manganese doped nickel hydroxide material at a current density of 0.1C.
FIG. 5 is a discharge curve of a 15 wt% redox graphene coated 10% (molar weight) manganese doped nickel hydroxide material at a current density of 0.1C.
Fig. 6 is a discharge curve of 6% (molar weight) manganese-doped nickel hydroxide and nickel hydroxide composite reduced graphene oxide at a current density of 0.1C.
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 a manganese-doped nickel hydroxide composite reduced graphene oxide zinc-nickel secondary battery anode material, which comprises the following steps:
step one, preparing a manganese-doped nickel hydroxide composite reduced graphene oxide material
Dissolving nickel sulfate and manganese sulfate in water, uniformly stirring, adding sodium hydroxide and ammonia water, uniformly stirring, adding graphite oxide, carrying out ultrasonic treatment on the mixture, transferring the obtained mixture into a reaction kettle, and carrying out hydrothermal reaction at a certain reaction temperature 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 manganese-doped nickel hydroxide composite reduced graphene oxide material.
The mass ratio of the nickel sulfate to the manganese sulfate is 1: 0.006-1: 0.215; the mass ratio of the nickel sulfate to the sodium hydroxide is 1: 0.3-1: 0.5; the mass ratio of the nickel sulfate to the ammonia water is 1: 0.05-1: 0.1; the mass ratio of the nickel sulfate to the graphite oxide is 1: 0.03-1: 0.1; the concentration of the nickel sulfate in water is 35 mg/mL-60 mg/mL;
the ultrasonic treatment time is 5-15 Min; the hydrothermal reaction temperature is 120-200 ℃, and the reaction time is 1-8 h. (ii) a
The vacuum drying temperature is 60-80 ℃, and the drying time is 8-12 h.
Step two, preparing the positive electrode of the zinc-nickel secondary battery
Weighing a certain amount of prepared manganese-doped nickel hydroxide composite reduced graphene oxide material, mixing the manganese-doped nickel hydroxide composite reduced graphene oxide material with conductive carbon black and polyvinylidene fluoride according to the mass ratio of 8:1: 1-7: 1.5:1.5, fully grinding, dropwise adding a proper amount of N-methyl-2-pyrrolidone into a dropper, fully stirring, coating the uniformly mixed electrode material on foamed nickel, and drying for 4-6 hours at the temperature of 60-80 ℃ by using a forced air drying oven. Mixing zinc oxide, zinc powder, bismuth trioxide and polytetrafluoroethylene according to the proportion of 80:12:3:5, dropwise adding a small amount of water, uniformly stirring, coating the mixture on a tin-plated copper net, drying for 4-6 hours at the temperature of 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 the positive 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 a manganese-doped nickel hydroxide composite reduced graphene oxide material
2.3656g of nickel sulfate and 0.1695g of manganese sulfate were dissolved in 50mL of water, 0.9000g of sodium hydroxide and 0.2g of concentrated ammonia water (mass fraction: 25%) were added at the same time, the mixture was stirred for 5 minutes until uniform, 0.1g of graphite oxide was added, the reaction mixture was subjected to ultrasonic treatment, 10Min was added, and the resulting solution was transferred to a reaction kettle and reacted at 160 ℃ for 4 hours. And after the reaction kettle is cooled to room temperature, centrifugally washing the reaction kettle for 3 times by using deionized water, and then drying the reaction kettle for 10 hours at the temperature of 60 ℃ by using a vacuum drying oven to obtain the manganese-doped nickel hydroxide composite reduced graphene oxide material.
Step two, preparing the positive electrode of the zinc-nickel secondary battery
Weighing 80mg of the obtained manganese-doped nickel hydroxide composite reduced graphene oxide material, mixing the manganese-doped nickel hydroxide 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 3-5 drops of N-methyl-2-pyrrolidone by using a dropper, fully stirring, coating the uniformly mixed electrode material on foamed nickel, and drying for 6 hours at 80 ℃ by using a blast drying oven. Mixing zinc oxide, zinc powder, bismuth trioxide and polytetrafluoroethylene according to the proportion of 80:12:3:5, dripping a small amount of water, uniformly stirring, coating the mixture on a tin-plated copper net, drying for 6 hours at 80 ℃ by using a blast drying oven, and then using the dried mixture as a counter electrode, wherein the theoretical capacity of the electrode is more than 3 times of that of the positive 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 scanning electron micrograph of a synthesized 10 wt% redox graphene-coated 10% (molar weight) manganese-doped nickel hydroxide material, and it can be seen that the material has a nanosheet structure, the particle size of the nanosheet is about 60-100 nm, and the surface of the nanosheet is coated with the reduced graphene oxide.
Fig. 2 is an XRD picture of the synthesized 10 wt% redox graphene coated 10% (molar weight) manganese doped nickel hydroxide material. The figure shows samples having characteristic peaks (001), (100), (101), (102), (110), (003), (111), (200), (103), (201) and the like typical of β -type nickel hydroxide, demonstrating that the synthesized samples are a beta-type nickel hydroxide; and no characteristic peak of manganese oxide appears, which proves that the manganese element is doped into the nickel hydroxide crystal lattice.
FIG. 3 shows that the synthesized 10 wt% redox graphene coated 10% (molar weight) manganese doped nickel hydroxide material is 105mg/cm2Specific discharge capacity and area capacity curves at current densities of 0.1C and 3C under high load conditions. As can be seen from the figure, the prepared material still has the specific discharge capacity of 224.6mAh g under the current density of 0.1C-1The specific discharge capacity of the material reaches 165.6mAh g when the surface capacity reaches 23.6mAh and the current density of 3C-1。
Example 2
Step one, preparing a manganese-doped nickel hydroxide composite reduced graphene oxide material
2.4708g of nickel sulfate and 0.1014g of manganese sulfate were dissolved in 50mL of water, 0.9000g of sodium hydroxide and 0.2g of concentrated ammonia water (mass fraction of 25%) were added at the same time, the mixture was stirred for several minutes until uniform, 0.1g of graphite oxide was added, the reaction mixture was then subjected to ultrasonic treatment, 10Min was added, and the resulting solution was transferred to a reaction vessel and reacted at 160 ℃ for 4 hours. 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 manganese-doped nickel hydroxide composite reduced graphene oxide material.
Step two, preparing the positive electrode of the zinc-nickel secondary battery
Weighing 80mg of the obtained manganese-doped nickel hydroxide composite reduced graphene oxide material, mixing the manganese-doped nickel hydroxide 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 3-5 drops of N-methyl-2-pyrrolidone by using a dropper, fully stirring, coating the uniformly mixed electrode material on foamed nickel, and drying for 6 hours at 80 ℃ by using a blast drying oven. Mixing zinc oxide, zinc powder, bismuth trioxide and polytetrafluoroethylene according to the proportion of 80:12:3:5, dripping a small amount of water, uniformly stirring, coating the mixture on a tin-plated copper net, drying for 6 hours at 80 ℃ by using a blast drying oven, and then using the dried mixture as a counter electrode, wherein the theoretical capacity of the electrode is more than 3 times of that of the positive 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 manganese doping is reduced to 6%. The discharge curve of the electrode material at a current density of 0.1C 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 the doping amount of manganese is too large, which affects the amount of nickel hydroxide produced and the conductivity, and thus the electrochemical performance. By comparison, it can be found that 10% is a better manganese doping ratio.
Example 3
Step one, preparing a manganese-doped nickel hydroxide composite reduced graphene oxide material
2.3656g of nickel sulfate and 0.1695g of manganese sulfate were dissolved in 50mL of water, 0.9000g of sodium hydroxide and 0.2g of concentrated ammonia water (mass fraction: 25%) were added at the same time, the mixture was stirred for several minutes until uniform, 0.1675g of graphite oxide was added, the reaction mixture was subjected to ultrasonic treatment, 10Min was added, and the resulting solution was transferred to a reaction kettle and reacted at 160 ℃ for 4 hours. 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 manganese-doped nickel hydroxide composite reduced graphene oxide material.
Step two, preparing the positive electrode of the zinc-nickel secondary battery
Weighing 80mg of the obtained manganese-doped nickel hydroxide composite reduced graphene oxide material, mixing the manganese-doped nickel hydroxide 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 3-5 drops of N-methyl-2-pyrrolidone by using a dropper, fully stirring, coating the uniformly mixed electrode material on foamed nickel, and drying for 6 hours at 80 ℃ by using a blast drying oven. Mixing zinc oxide, zinc powder, bismuth trioxide and polytetrafluoroethylene according to the proportion of 80:12:3:5, dripping a small amount of water, uniformly stirring, coating the mixture on a tin-plated copper net, drying for 6 hours at 80 ℃ by using a blast drying oven, and then using the dried mixture as a counter electrode, wherein the theoretical capacity of the electrode is more than 3 times of that of the positive 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 is essentially the same as the method employed in example 1, except that the amount of coated redox graphene was changed to 15%. The discharge curve of the electrode material at a current density of 0.1C 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 coated redox graphene in the synthesized composite material affects the proportion of the active material nickel hydroxide in the whole material, which in turn affects its performance.
Comparative example 1
Step one, preparing nickel hydroxide material
2.6905g of nickel sulfate was dissolved in 50mL of water, 0.9000g of sodium hydroxide and 0.2g of concentrated ammonia (mass fraction: 25%) were added, the reaction mixture was subjected to ultrasonic treatment after stirring for several minutes until uniform, and after 10Min, the resulting solution was transferred to a reaction vessel and reacted at 160 ℃ for 4 hours. 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 nickel hydroxide material.
Step two, preparing the positive electrode of the zinc-nickel secondary battery
Weighing 80mg of the obtained nickel hydroxide material, mixing the nickel hydroxide material with conductive carbon black and a binding agent polyvinylidene fluoride according to a 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 foamed nickel, and drying for 6 hours at 80 ℃ by using a blast drying oven. Mixing zinc oxide, zinc powder, bismuth trioxide and polytetrafluoroethylene according to the proportion of 80:12:3:5, dripping a small amount of water, uniformly stirring, coating the mixture on a tin-plated copper net, drying for 6 hours at 80 ℃ by using a blast drying oven, and then using the dried mixture as a counter electrode, wherein the theoretical capacity of the electrode is more than 3 times of that of the positive 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 manganese doping is performed and no reduction of graphene oxide is performed. The discharge curve of the electrode material at a current density of 0.1C 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 manganese doping and the reduced graphene oxide coating can enhance the conductivity of the nickel hydroxide material, and then affect the specific discharge capacity thereof. Through comparison, the material obtained by carrying out manganese doping and coating reduction on graphene oxide has better performance.
Comparative example 2
Step one, preparing nickel hydroxide material
2.3656g of nickel sulfate and 0.1695g of manganese sulfate are dissolved in 50mL of water, 0.9000g of sodium hydroxide is added, after stirring for a few minutes until uniform, 0.2g of concentrated ammonia water (mass fraction of 25%) is added, after stirring for 5 minutes until uniform, 0.1g of graphite oxide is added, then the reactants are subjected to ultrasonic treatment, after 10Min, the obtained solution is transferred to a reaction kettle and reacted for 4 hours at 160 ℃. 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 nickel hydroxide material.
Step two, preparing the positive electrode of the zinc-nickel secondary battery
Weighing 80mg of the obtained nickel hydroxide material, mixing the nickel hydroxide material with conductive carbon black and a binding agent polyvinylidene fluoride according to a 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 foamed nickel, and drying for 6 hours at 80 ℃ by using a blast drying oven. Mixing zinc oxide, zinc powder, bismuth trioxide and polytetrafluoroethylene according to the proportion of 80:12:3:5, dripping a small amount of water, uniformly stirring, coating the mixture on a tin-plated copper net, drying for 6 hours at 80 ℃ by using a blast drying oven, and then using the dried mixture as a counter electrode, wherein the theoretical capacity of the electrode is more than 3 times of that of the positive 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 sodium hydroxide and aqueous ammonia were not added simultaneously during the reaction. Under the same current density of the electrode material and the material prepared in the example 1, the specific discharge capacity of the material prepared by the method adopted in the comparative example is far lower than that of the material prepared in the example 1. The reason is that sodium hydroxide and ammonia water are not added simultaneously, which is not beneficial to controlling the PH value in the reaction process and influencing the crystallinity of the material, so that the specific discharge capacity of the material is lowered. Through comparison, the material obtained by carrying out manganese doping and coating reduction on graphene oxide has better performance.
Comparative example 3
Step one, manganese-doped nickel hydroxide material preparation
2.3656g of nickel sulfate and 0.1695g of manganese sulfate were dissolved in 50mL of water, 0.9000g of sodium hydroxide and 0.2g of concentrated ammonia water were added at the same time, the mixture was stirred for several minutes until uniform, and then the reaction mixture was subjected to ultrasonic treatment, 10Min was followed by transferring the resulting solution to a reaction vessel and reacting at 160 ℃ for 4 hours. 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 for 10 hours at the temperature of 60 ℃ by using a vacuum drying oven to obtain the manganese-doped nickel hydroxide material. Step two, preparing the positive electrode of the zinc-nickel secondary battery
Weighing 80mg of the obtained manganese-doped nickel hydroxide material, mixing the manganese-doped nickel hydroxide 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 foamed nickel, and drying for 6 hours at 80 ℃ by using a blast drying oven. Mixing zinc oxide, zinc powder, bismuth trioxide and polytetrafluoroethylene according to a ratio of 80:12:3:5, dripping a small amount of water, uniformly stirring, coating the mixture on a tin-plated copper mesh, drying for 6 hours at 80 ℃ by using a blast drying oven, and then using the tin-plated copper mesh as a counter electrode to ensure that the theoretical capacity of the electrode is more than 3 times of the theoretical capacity of the positive 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 graphene coating is not performed. The discharge curve of the electrode material at a current density of 0.1C 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 coating of the reduced graphene oxide can enhance the conductivity of the nickel hydroxide material, which in turn affects the specific discharge capacity thereof. Through comparison, the material obtained by coating the reduced graphene oxide has better performance.
Comparative example 4
Step one, preparing a manganese-doped nickel hydroxide composite reduced graphene oxide material
2.1816g of nickel sulfate and 0.4563g of manganese sulfate were dissolved in 50mL of water, 0.9000g of sodium hydroxide and 0.2g of concentrated ammonia water were added at the same time, the mixture was stirred for several minutes until uniform, 0.1g of graphite oxide was added, the reaction mixture was subjected to ultrasonic treatment, 10Min was added, and the resulting solution was transferred to a reaction vessel and reacted at 160 ℃ for 4 hours. 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 manganese-doped nickel hydroxide composite reduced graphene oxide material.
Step two, preparing the positive electrode of the zinc-nickel secondary battery
Weighing 80mg of the obtained manganese-doped nickel hydroxide composite reduced graphene oxide material, mixing the manganese-doped nickel hydroxide 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 3-5 drops of N-methyl-2-pyrrolidone by using a dropper, fully stirring, coating the uniformly mixed electrode material on foamed nickel, and drying for 6 hours at 80 ℃ by using a blast drying oven. Mixing zinc oxide, zinc powder, bismuth trioxide and polytetrafluoroethylene according to a ratio of 80:12:3:5, dripping a small amount of water, uniformly stirring, coating the mixture on a tin-plated copper mesh, drying for 6 hours at 80 ℃ by using a blast drying oven, and then using the tin-plated copper mesh as a counter electrode to ensure that the theoretical capacity of the electrode is more than 3 times of the theoretical capacity of the positive 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 was essentially the same as that used in example 1 except that the manganese doping was increased to 27%. 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 the doping amount of manganese affects the proportion of the active material nickel hydroxide in the material, and further affects the electrochemical performance of the material.
Comparative example 5
Step one, preparing a manganese-doped nickel hydroxide composite reduced graphene oxide material
2.3656g of nickel sulfate and 0.1695g of manganese sulfate were dissolved in 50mL of water, 0.9000g of sodium hydroxide and 0.2g of concentrated ammonia water were added at the same time, the mixture was stirred for several minutes until uniform, 0.0285g of graphite oxide was added, the reaction mixture was then subjected to ultrasonic treatment, and after 10Min, the resulting solution was transferred to a reaction vessel and reacted at 160 ℃ for 4 hours. 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 manganese-doped nickel hydroxide composite reduced graphene oxide material.
Step two, preparing the positive electrode of the zinc-nickel secondary battery
Weighing 80mg of the obtained manganese-doped nickel hydroxide composite reduced graphene oxide material, mixing the manganese-doped nickel hydroxide 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 3-5 drops of N-methyl-2-pyrrolidone by using a dropper, fully stirring, coating the uniformly mixed electrode material on foamed nickel, and drying for 6 hours at 80 ℃ by using a blast drying oven. Mixing zinc oxide, zinc powder, bismuth trioxide and polytetrafluoroethylene according to the proportion of 80:12:3:5, dripping a small amount of water, uniformly stirring, coating the mixture on a tin-plated copper net, drying for 6 hours at 80 ℃ by using a blast drying oven, and then using the dried mixture as a counter electrode, wherein the theoretical capacity of the electrode is more than 3 times of that of the positive 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 is essentially the same as the method used in example 1, except that the amount of coated reduced graphene oxide is reduced to 3%. 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 too little amount of the coated reduced graphene oxide reduces the conductivity of the composite material, resulting in a reduction in the specific capacity of the material.
Comparative example 6
Step one, preparing a manganese-doped nickel hydroxide composite reduced graphene oxide material
2.3656g of nickel sulfate and 0.1695g of manganese sulfate were dissolved in 50mL of water, 0.9000g of sodium hydroxide and 0.2g of concentrated ammonia water were added at the same time, the mixture was stirred for several minutes until uniform, 0.1g of graphite oxide was added, then the reaction mixture was subjected to ultrasonic treatment, 10Min was added, and the resulting solution was transferred to a reaction kettle and reacted at 160 ℃ for 0.5 h. 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 manganese-doped nickel hydroxide composite reduced graphene oxide material.
Step two, preparing the positive electrode of the zinc-nickel secondary battery
Weighing 80mg of the obtained manganese-doped nickel hydroxide composite reduced graphene oxide material, mixing the manganese-doped nickel hydroxide 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 3-5 drops of N-methyl-2-pyrrolidone by using a dropper, fully stirring, coating the uniformly mixed electrode material on foamed nickel, and drying for 6 hours at 80 ℃ by using a blast drying oven. Mixing zinc oxide, zinc powder, bismuth trioxide and polytetrafluoroethylene according to the proportion of 80:12:3:5, dripping a small amount of water, uniformly stirring, coating the mixture on a tin-plated copper net, drying for 6 hours at 80 ℃ by using a blast drying oven, and then using the dried mixture as a counter electrode, wherein the theoretical capacity of the electrode is more than 3 times of that of the positive 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 to 0.5 hours. 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 synthesized material, and too short a reaction time deteriorates the crystallinity, thereby affecting the performance.
Comparative example 7
Step one, preparing a manganese-doped nickel hydroxide composite reduced graphene oxide material
2.3656g of nickel sulfate and 0.1695g of manganese sulfate are dissolved in 50mL of water, 0.9000g of sodium hydroxide and 0.2g of concentrated ammonia water are added at the same time, the mixture is stirred for a few minutes until uniform, 0.1g of graphite oxide is added, then the reaction mass is subjected to ultrasonic treatment, 10Min of the obtained solution is transferred to a reaction kettle, and the reaction is carried out for 4 hours at 80 ℃. 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 manganese-doped nickel hydroxide composite reduced graphene oxide material.
Step two, preparing the positive electrode of the zinc-nickel secondary battery
Weighing 80mg of the obtained manganese-doped nickel hydroxide composite reduced graphene oxide material, mixing the manganese-doped nickel hydroxide 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 3-5 drops of N-methyl-2-pyrrolidone by using a dropper, fully stirring, coating the uniformly mixed electrode material on foamed nickel, and drying for 6 hours at 80 ℃ by using a blast drying oven. Mixing zinc oxide, zinc powder, bismuth trioxide and polytetrafluoroethylene according to the proportion of 80:12:3:5, dripping a small amount of water, uniformly stirring, coating the mixture on a tin-plated copper net, drying for 6 hours at 80 ℃ by using a blast drying oven, and then using the dried mixture as a counter electrode, wherein the theoretical capacity of the electrode is more than 3 times of that of the positive 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 temperature of the hydrothermal reaction was changed to 80 ℃. 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 temperature affects the crystallinity of the synthesized material and the degree of reduction of the coated reduced graphene oxide, which in turn affects the performance thereof.
Comparative example 8
Step one, manganese-doped nickel hydroxide material preparation
2.3656g of nickel sulfate and 0.1695g of manganese sulfate were dissolved in 50mL of water, 0.9000g of sodium hydroxide and 0.2000g of concentrated ammonia water were added at the same time, the mixture was stirred for several minutes until uniform, and then the reaction mixture was subjected to ultrasonic treatment, 10Min was followed by transferring the resulting solution to a reaction vessel and reacting at 160 ℃ for 4 hours. 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 manganese-doped nickel hydroxide composite reduced graphene oxide material.
Step two, preparing the positive electrode of the zinc-nickel secondary battery
Weighing 80mg of the obtained manganese-doped nickel hydroxide material, mixing the manganese-doped nickel hydroxide 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 0.1000g of reduced graphene oxide, dropwise adding 3-5 drops of N-methyl-2-pyrrolidone by a dropper, fully stirring, coating the uniformly mixed electrode material on foamed nickel, and drying for 6 hours at 80 ℃ by using a blast drying oven. Mixing zinc oxide, zinc powder, bismuth trioxide and polytetrafluoroethylene according to the proportion of 80:12:3:5, dripping a small amount of water, uniformly stirring, coating the mixture on a tin-plated copper net, drying for 6 hours at 80 ℃ by using a blast drying oven, and then using the dried mixture as a counter electrode, wherein the theoretical capacity of the electrode is more than 3 times of that of the positive 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 essentially the same as that used in example 1, except that manganese-doped nickel hydroxide is physically mixed with reduced graphene oxide. The material prepared by the method of this comparative example has a lower specific discharge capacity than that of example 1 at the same current density. This is because physical mixing is difficult to achieve as uniform as the surface coating of the material, which in turn affects its performance.

Claims (10)

1. The manganese-doped nickel hydroxide composite reduced graphene oxide material is characterized in that:
manganese replaces the position of part of nickel in the nickel hydroxide crystal lattice to obtain manganese-doped nickel hydroxide; the reduced graphene oxide is coated on the surface of a manganese-doped nickel hydroxide nanosheet to obtain a manganese-doped nickel hydroxide composite reduced graphene oxide material, namely a composite material;
the atomic ratio of manganese element to nickel element in the manganese-doped nickel hydroxide is 0.01: 1-0.25: 1 (preferably 0.05: 1-0.15: 1, and the mass ratio is 0.0093: 1-0.2339: 1); the reduced graphene oxide accounts for 5-25% (preferably 10-20%) of the total mass of the composite material.
2. The manganese-doped nickel hydroxide composite reduced graphene oxide material according to claim 1, wherein: the crystal form of the nickel hydroxide is beta type;
and substituting manganese for part of nickel positions in the nickel hydroxide crystal lattice by using manganese through a hydrothermal synthesis method to obtain the manganese-doped nickel hydroxide.
3. The manganese-doped nickel hydroxide composite reduced graphene oxide material according to claim 1, wherein: the particle size of the manganese-doped nickel hydroxide nanosheet in the composite material is 60-100 (preferably 70-80) nanometers, and the surface of the manganese-doped nickel hydroxide nanosheet is coated with reduced graphene oxide.
4. The manganese-doped nickel hydroxide composite reduced graphene oxide material according to claim 1, characterized in that: the thickness of the reduced graphene oxide coated on the surface is 5-8 nanometers.
5. A preparation method of the manganese-doped nickel hydroxide composite reduced graphene oxide material as claimed in any one of claims 1 to 4, is characterized in that:
dissolving nickel sulfate and manganese sulfate in water, uniformly stirring, adding sodium hydroxide and ammonia water, uniformly stirring, adding graphite oxide, carrying out ultrasonic treatment on the mixture, and transferring the obtained mixture to a reaction kettle for hydrothermal reaction; cooling to room temperature, centrifugally washing for more than 3 times by using deionized water, and drying by using a vacuum drying oven to finally obtain the manganese-doped nickel hydroxide composite reduced graphene oxide material;
the mass ratio of the nickel sulfate to the manganese sulfate is 1: 0.006-1: 0.215; the mass ratio of the nickel sulfate to the sodium hydroxide is 1: 0.3-1: 0.5; the mass ratio of the nickel sulfate to the ammonia water is 1: 0.05-1: 0.1; the mass ratio of the nickel sulfate to the graphite oxide is 1: 0.03-1: 0.1; the concentration of the nickel sulfate in the water is 35 mg/mL-60 mg/mL.
6. The method of claim 5, wherein:
the ultrasonic treatment time is 5-15 Min; the hydrothermal reaction temperature is 120-200 ℃, and the reaction time is 1-8 h.
7. The method of claim 5, wherein: the mass concentration of ammonia water is 25%.
8. The method of claim 5, wherein:
the vacuum drying temperature is 60-80 ℃, and the drying time is 8-12 h.
9. The application of the manganese-doped nickel hydroxide composite reduced graphene oxide material as an anode active material in a cathode of a zinc-nickel secondary battery according to any one of claims 1 to 4.
10. Use according to claim 9, characterized in that:
the positive electrode material of the zinc-nickel secondary battery comprises the following components in percentage by mass: 1: 1-7: 1.5:1.5 manganese-doped nickel hydroxide composite graphene material, conductive carbon black and a binder polyvinylidene fluoride.
CN202011344870.2A 2020-11-26 2020-11-26 Manganese-doped nickel hydroxide composite reduced graphene oxide material, preparation and application Pending CN114551859A (en)

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CN108597890A (en) * 2018-04-23 2018-09-28 上海应用技术大学 A kind of polyaniline/graphene/nickel manganese hydroxide electrode material for super capacitor and preparation method thereof
CN110085440A (en) * 2019-04-23 2019-08-02 中国计量大学 A kind of nickel hydroxide/redox graphene electrode material preparation method
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1383587A (en) * 2000-06-16 2002-12-04 松下电器产业株式会社 Anode active material for alkali storage battery, anode including samd, and alkali storage battery
CN1467160A (en) * 2002-07-08 2004-01-14 湘潭大学 Method for preparing spherical nickel hydroxide having high power charging-discharging ability
CN102249349A (en) * 2011-04-26 2011-11-23 北京化工大学 Multi-component doped spherical nano nickel hydroxide synthesized by chemical-electrochemical combined method
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