CN102426926A - A kind of preparation method of supercapacitor and battery composite cathode material - Google Patents

Abstract

A method for preparing a composite positive electrode material for a supercapacitor and a battery mainly comprises the following steps: a rotating barrel connected to a motor is arranged in a liquid storage tank, one end of which is provided with a liquid inlet pipe connected to a circulation pump, and a power supply and an ammeter are connected in series to form a power supply assembly. The power supply assembly is connected to the rotating barrel and the liquid inlet pipe to form a circuit. The liquid storage tank is filled with an electrolyte with a concentration of 0.05-5.5 mol·dm ^-3 , and 0-100 g·dm ^-3 of a nano carbon material is added to the electrolyte. Electrodeposition is performed at a current density of 0.5-500 mA·cm ^-2 and a temperature of 15-90°C. The material prepared by the method has a large number of nano-micropores, high specific capacity, good electronic conductivity, high rate charge and discharge, low cost, simple operation, low environmental pollution, short preparation time, and easy control.

Description

A kind of preparation method of supercapacitor and battery composite cathode material

technical field

The invention relates to a preparation method of an electrode material.

Background technique

It is now known that the active electrode material is one of the main factors determining the performance of supercapacitors or batteries. Among the active materials of various supercapacitors, nano-manganese dioxide and nickel hydroxide with high specific surface area (and nickel hydroxide heat-treated The prepared nickel oxide, the same below) as a supercapacitor positive electrode material, used to replace activated carbon and noble metal oxides has attracted widespread attention and has great development potential.

Both manganese dioxide and nickel hydroxide are semiconductor materials with a wide band gap and poor electronic conductivity. Therefore, it is necessary to compound a certain amount of nano-carbon materials inside the material to support their work. These nano-carbon materials themselves have certain dual properties. Electric layer capacitance, its more important role is to provide electronic conductivity for the electrochemical reaction of manganese dioxide and nickel hydroxide, which can significantly improve the structure and comprehensive performance of manganese dioxide and nickel hydroxide materials.

The preparation technology of manganese dioxide/carbon and nickel hydroxide/carbon composites and their application in supercapacitors are currently hot issues in the field of nanomaterial chemistry at home and abroad. The research work reported in the existing literature basically uses chemical methods to deposit a certain amount of manganese dioxide or nickel hydroxide on the surface of nanocarbon materials such as carbon nanotubes, graphene, and activated carbon. The prepared composite material has the problems of uneven distribution of nano-carbon in transition metal oxide, insufficient contact between transition metal oxide and nano-carbon material, and poor uniformity and controllability of micropores in the composite material, which leads to its performance Also need to improve, can't satisfy people's demand.

Contents of the invention

The purpose of the present invention is to provide a supercapacitor and battery that can make nano-carbon materials evenly distributed in transition metal oxides, facilitate ion conduction and liquid-phase mass transfer in electrolytes, and can significantly improve the electrochemical performance of composite positive electrode materials The preparation method of the composite cathode material. The invention mainly adopts the method of supergravity electrodeposition to prepare transition metal oxide/carbon composite material.

Technical scheme of the present invention is as follows:

1. Preparation device

The device of the present invention is mainly composed of a liquid storage tank, a rotating barrel, a motor and a circulation pump. A cylindrical shell-shaped rotating barrel is arranged on the upper part of the liquid storing tank as a supergravity reactor. The rotating barrel is made of corrosion-resistant metal The inner wall of the barrel in contact with the electrolyte is preferably provided with a guide plate to control the flow direction of the fluid. It is better to coat the inner wall of the barrel with a catalytic coating such as platinum as an electrode for electrochemical reactions. Preferably, another metal inner cylinder convenient for cleaning is provided in the rotating barrel, and the inner wall of the metal inner cylinder is plated with a platinum coating. One end surface of the above-mentioned rotary bucket is provided with a reduced diameter, which is sealed and connected with the horizontal shaft of the motor outside the liquid storage tank, so that the motor can drive it to rotate; the other end surface of the rotary bucket is provided with a central through hole, and an opening is inserted in the central through hole The horizontal liquid inlet pipe installed in the rotating barrel, the other end of the fixed liquid inlet pipe protrudes out of the liquid storage tank and connects with the liquid outlet of the circulation pump, and the liquid inlet of the circulation pump is connected with the outlet at the bottom of the liquid storage tank. The liquid pipe is connected. A heating mechanism and a temperature display mechanism are arranged in the liquid storage tank. There is also a DC power supply or a pulse power supply connected in series with an ammeter to form a power supply component.

2. Preparation method

(1) Connect the power supply assembly with the rotating barrel and the liquid inlet pipe to form a circuit. When preparing manganese dioxide/carbon, the inner wall of the rotating barrel is connected to the positive electrode of the power supply, and the liquid inlet pipe is connected to the negative electrode of the power supply; when preparing nickel hydroxide/carbon Then vice versa, the inner wall of the rotary barrel is connected with the negative pole of the power supply, and the liquid inlet pipe is connected with the positive pole of the power supply.

(2) Electrolyte is housed in the above-mentioned liquid storage tank, which can be a soluble salt solution of divalent manganese ions, and the salt solution of divalent manganese ions can be any one or two solutions of manganese sulfate and manganese acetate. Mix; this electrolytic solution can also be the soluble salt solution of divalent nickel ion, and the salt solution of described divalent nickel ion can be any one or more solutions in nickel nitrate, nickel sulfate, nickel acetate, nickel sulfamate the mix of. The concentration of the above electrolytic solution is 0.05 mol/dm ³ -4.5 mol/dm ³ . Add 0-100g/ ^dm3 nano-carbon material to the electrolyte, and the nano-carbon material can be carbon nanotube, graphene, activated carbon, acetylene black, nano-graphite powder or carbon aerogel.

(3) Turn on the DC or pulse power supply to output a current density of 0.5mA/cm ² to 500mA/cm ² on the inner wall of the rotating barrel, and conduct electrodeposition at a temperature of 15°C to 90°C. The strength of the supergravity field generated by the electrodeposition device is expressed in multiples of the strength of the earth's surface gravity field. The calculation formula is as follows: supergravity field strength=[(2πn/60) ² ×R/ g]g. Among them, n is the rotational speed of the rotating barrel per minute, R is the radius of the inner wall of the rotating barrel in meters, and g is the gravitational acceleration on the earth's surface, and its value is 9.8 m/s ² . Adjust the rotational speed and diameter of the rotating barrel to control the strength of the supergravity field within the range of 1g-1000g ((g=9.8m·s ^-2 )).

(4) According to different electrodeposition conditions, the electrodeposition products formed by electrodeposition have different forms:

a. Suspended in the electrolyte, the electrodeposition process can be carried out continuously, and the electrodeposition products can be collected through a filter device, cleaned and dried for later use;

b. If it is attached to the electrode on the inner wall of the rotating barrel, stop the machine after a certain period of electrodeposition (generally 1 to 5 hours), scrape off, clean and dry the electrodeposited product for later use.

(5) The prepared transition metal oxide/carbon composite material is mixed with 5-15wt% acetylene black, and pressed into sheets to make the positive electrode of a supercapacitor or battery.

The invention adopts the method of supergravity electrodeposition to prepare the transition metal oxide/carbon composite material. In the electrolyte solution containing Mn ²⁺ or Ni ²⁺ , add a certain amount of nano-carbon material, form a supergravity field through the high-speed rotation of the cylindrical reaction chamber, and use a corrosion-resistant pump as a circulation pump to make the electrolyte flow in the rotating barrel The method of circulating between the positive and negative electrodes and forming a stable electrolyte flow between the positive and negative electrodes realizes high-speed electrodeposition under high gravity. By adjusting the rotational speed and diameter of the rotating barrel, the intensity of the supergravity field can be adjusted. As the strength of the supergravity field increases, the radial convection velocity of the electrolyte increases accordingly. Since the limiting diffusion current density of electrodeposition is proportional to the 1/2 power of the electrolyte flow rate, the overpotential and current density of electrodeposition can be increased without concentration polarization. At high potential, the nucleation speed of electrodeposition is greatly accelerated, so the structure of the deposited layer is refined, and a transition metal oxide/carbon composite material with three-dimensional nano-micropores and nano-carbon conductive networks interlaced and with a high specific surface area can be prepared. The composite material is used as the positive electrode material of supercapacitor and battery.

For the nano-carbon material suspended in the electrolyte, because its density is much higher than that of the electrolyte, under the action of the supergravity field, the nano-carbon material will be in the rotating barrel under the action of the normal force it receives. The surface of the inner wall is enriched and covered by continuously deposited manganese dioxide or nickel hydroxide.

The advantages of the present invention are as follows:

1. The micro-morphology of the prepared transition metal oxide/carbon composite material is a three-dimensional nano-micropore and nano-carbon conductive network interlaced structure, as shown in Figure 2. This kind of material has a large number of nano-micropores, so it has a high specific surface area, so the specific capacity of the material can be improved.

2. The three-dimensional microporous network structure is conducive to the mass transfer and electromigration in the electrolyte, which is beneficial to the electrochemical reaction. At the same time, nano-carbon materials are also uniformly distributed in the transition metal oxide material in a three-dimensional network, which is conducive to improving the electronic conductivity of the material.

3. Low cost, easy operation, high-rate charging and discharging, less environmental pollution, unlimited samples, short preparation time and easy control.

Description of drawings

Fig. 1 is a schematic diagram of the structure of the preparation device of the present invention.

Figure 2 is an electron micrograph of the manganese dioxide/carbon nanotube composite material prepared in the present invention.

Detailed ways

In the preparation device of the present invention shown in Fig. 1, a cylindrical shell-shaped rotary barrel 2 is arranged on the upper part of the liquid storage tank 1, and the rotary barrel is made of corrosion-resistant metal materials. The rotating bucket is provided with a deflector 3 for controlling the flow direction of the fluid; the inside of the bucket is lined with a metal inner cylinder 4, and the inside of the metal inner cylinder is coated with catalytic coatings such as platinum. One end face of the above-mentioned rotating barrel is provided with a reduced diameter, which is sealed and connected with the horizontal shaft of the motor 5 outside the liquid storage tank, and the other end face of the rotating barrel is provided with a central through hole, which is inserted with an opening in the rotating barrel. Horizontal liquid inlet pipe 6, the fixed liquid inlet pipe, its other end stretches out of the liquid storage tank and is connected with the liquid outlet of circulation pump 7, and the liquid inlet of this circulation pump links to each other with the liquid outlet pipe at the bottom of the liquid storage tank. A heating mechanism 8 and a temperature display mechanism 9 are arranged in the liquid storage tank. Another DC power supply or pulse power supply is connected in series with the ammeter 10 to form a power supply assembly.

Example 1

The above power supply assembly is connected with the rotating barrel and the liquid inlet pipe to form a circuit, the inner wall of the rotating barrel is connected to the positive pole of the power supply, and the liquid inlet pipe is connected to the negative pole of the power supply. The liquid storage tank is filled with a manganese acetate solution with a concentration of 0.05 mol/dm ³ , and 60 g/L multi-walled carbon nanotube carbon material dispersed in the electrolyte solution is added. The calculation formula of the supergravity field strength generated by the electrodeposition is as follows: supergravity field strength=[(2πn/60) ² ×R/ g]g. Among them, n is 300 rpm, R is 50mm, g is 9.8 m/s ² , and the supergravity field strength can be calculated as 10g (g=9.8m·s ^-2 ). Turn on the DC power supply to output a current density of 0.8mA/cm ² to the inner wall of the rotating barrel, and conduct electrodeposition at a temperature of 40°C. Stop the machine after 1 hour of electrodeposition, scrape off, clean and dry the prepared electrodeposited product for later use. The electrodeposited product powder collected above was mixed with 10wt% acetylene black, pressed into sheets to make an electrode, and assembled into a supercapacitor. The positive electrode was tested for capacity. The specific capacity of the prepared manganese dioxide was 358.2F/g.

Example 2

The above power supply assembly is connected with the rotating barrel and the liquid inlet pipe to form a circuit, the inner wall of the rotating barrel is connected to the positive pole of the power supply, and the liquid inlet pipe is connected to the negative pole of the power supply. The manganese sulfate solution with a concentration of 3.5 mol/ ^dm3 is housed in the liquid storage tank, and 10 g/L graphene dispersed is added to the electrolytic solution. The calculation formula of the supergravity field strength generated by the electrodeposition is as follows: supergravity field strength=[(2πn/60) ² ×R/ g]g. Wherein, n is 1000 rpm, R is 50 mm, and g is 9.8 m/s ² . It can be calculated that the supergravity field strength is 100g (g=9.8m·s ^-2 ). Turn on the pulse power supply, the pulse frequency is 600Hz, the duty cycle is 60%, and the current density output to the inner wall of the rotating barrel is 0.5mA/cm ² , and the electrodeposition is carried out at a temperature of 80°C. Stop the machine after 1 hour of electrodeposition, scrape off, clean and dry the prepared electrodeposited product for later use. The electrodeposited product powder collected above is mixed with 5wt% acetylene black, pressed into sheets to make an electrode, and assembled into a supercapacitor with it, and the positive electrode is tested for capacity, and the specific capacity of the prepared manganese dioxide is 385.6F/g .

Example 3

The above power supply assembly is connected with the rotating barrel and the liquid inlet pipe to form a circuit, the inner wall of the rotating barrel is connected to the positive pole of the power supply, and the liquid inlet pipe is connected to the negative pole of the power supply. The concentration of 3.5mol/ ^dm3 manganese sulfate and 0.15mol/dm3 manganese acetate solution is housed in the liquid storage tank, and dispersed 20g/L graphene is added to the electrolyte. The calculation formula of the supergravity field strength generated by the electrodeposition is as follows: supergravity field strength=[(2πn/60) ² ×R/ g]g. Among them, n is 1000 rpm, R is 50mm, g is 9.8 m/s ² , and the supergravity field strength can be calculated as 100g (g=9.8m·s ^-2 ). Turn on the pulse power supply, the pulse frequency is 300Hz, the duty ratio is 60%, the current density output to the inner wall of the rotating barrel is 25mA/cm ² , and the electrodeposition is carried out at a temperature of 60°C. Stop the machine after 1 hour of electrodeposition, scrape off, clean and dry the prepared electrodeposited product for later use. The electrodeposition product powder collected above was mixed with 8wt% acetylene black, pressed into sheets to make an electrode, and assembled into a supercapacitor. The positive electrode was tested for capacity. The specific capacity of the prepared manganese dioxide was 314.2F/g.

Example 4

The above power supply assembly is connected with the rotating barrel and the liquid inlet pipe to form a circuit, the inner wall of the rotating barrel is connected to the positive pole of the power supply, and the liquid inlet pipe is connected to the negative pole of the power supply. The above liquid storage tank is equipped with a nickel sulfate solution with a concentration of 3.5 mol/dm ³ , and 80 g/L of dispersed multi-walled carbon nanotubes are added to the electrolyte solution. The calculation formula of the supergravity field strength generated by the electrodeposition is as follows: supergravity field strength=[(2πn/60) ² ×R/ g]g. Among them, n is 1000 rpm, R is 50mm, g is 9.8 m/s ² , and the supergravity field strength can be calculated as 100g (g=9.8m·s ^-2 ). Turn on the pulse power supply, the pulse frequency is 300Hz, the duty cycle is 50%, the current density output to the inner wall of the rotating barrel is 3mA/cm ² , and the electrodeposition is carried out at a temperature of 15°C. Stop the machine after 1 hour of electrodeposition, scrape off, clean and dry the prepared electrodeposited product for later use. The electrodeposited product powder collected above is mixed with 6wt% acetylene black, pressed into sheets to make an electrode, and assembled into a supercapacitor, and the positive electrode is tested for capacity, and the specific capacity of the prepared manganese dioxide is 796.7F/g .

Example 5

The above power supply assembly is connected with the rotating barrel and the liquid inlet pipe to form a circuit, the inner wall of the rotating barrel is connected to the positive pole of the power supply, and the liquid inlet pipe is connected to the negative pole of the power supply. A nickel nitrate solution with a concentration of 4.2 mol/ ^dm3 is housed in the liquid storage tank, and 5 g/L of dispersed graphene is added to the electrolyte. The calculation formula of the supergravity field strength generated by the electrodeposition is as follows: supergravity field strength=[(2πn/60) ² ×R/ g]g. Among them, n is 4230 rpm, R is 50mm, g is 9.8 m/s ² , and the supergravity field strength can be calculated as 1000g (g=9.8m·s ^-2 ). Turn on the pulse power supply, the pulse frequency is 300Hz, the duty cycle is 50%, the current density output to the inner wall of the rotating barrel is 10mA/cm ² , and the electrodeposition is carried out at a temperature of 25°C. Stop the machine after 1 hour of electrodeposition, scrape off, clean and dry the prepared electrodeposited product for later use. The electrodeposited product powder collected above is mixed with 12wt% acetylene black, pressed into sheets to make an electrode, and assembled into a supercapacitor, and the positive electrode is tested for capacity, and the specific capacity of the prepared manganese dioxide is 837.5F/g .

Example 6

The above power supply assembly is connected with the rotating barrel and the liquid inlet pipe to form a circuit, the inner wall of the rotating barrel is connected to the positive pole of the power supply, and the liquid inlet pipe is connected to the negative pole of the power supply. The liquid storage tank is filled with a nickel acetate solution with a concentration of 1.5 mol/dm ³ , and 100 g/L multi-walled carbon nanotube carbon material dispersed in the electrolyte solution is added. The calculation formula of the supergravity field strength generated by the electrodeposition is as follows: supergravity field strength=[(2πn/60) ² ×R/ g]g. Wherein, n is 300 rpm, R is 50 mm, and g is 9.8 m/s ² . It can be calculated that the supergravity field strength is 10g (g=9.8m·s ^-2 ). Turn on the DC power supply to output a current density of 100mA/cm ² to the inner wall of the rotating barrel, and conduct electrodeposition at a temperature of 50°C. Stop the machine after 1 hour of electrodeposition, scrape off, clean and dry the prepared electrodeposited product for later use. The electrodeposited product powder collected above is mixed with 15wt% acetylene black, pressed into sheets to make an electrode, and assembled into a supercapacitor, and the positive electrode is tested for capacity, and the specific capacity of the prepared manganese dioxide is 831.6F/g .

Example 7

The above power supply assembly is connected with the rotating barrel and the liquid inlet pipe to form a circuit, the inner wall of the rotating barrel is connected to the positive pole of the power supply, and the liquid inlet pipe is connected to the negative pole of the power supply. The above-mentioned liquid storage tank is equipped with a nickel sulfamate solution with a concentration of 4.0mol/dm ³ , and 50g/L of dispersed nano-graphite powder is added to the electrolytic solution. The calculation formula of the supergravity field strength generated by the electrodeposition is as follows: supergravity field strength=[(2πn/60) ² ×R/ g]g. Wherein, n is 4230 rpm, R is 50 mm, and g is 9.8 m/s ² . It can be calculated that the supergravity field strength is 1000g (g=9.8m·s ^-2 ). Turn on the pulse power supply, the pulse frequency is 400Hz, the duty cycle is 50%, the current density output to the inner wall of the rotating barrel is 300mA/cm ² , and the electrodeposition is carried out at a temperature of 60°C. Stop the machine after 1 hour of electrodeposition, scrape off, clean and dry the prepared electrodeposited product for later use. The electrodeposited product powder collected above is mixed with 11wt% acetylene black, pressed into sheets to make an electrode, and assembled into a supercapacitor, and the positive electrode is tested for capacity, and the specific capacity of the prepared manganese dioxide is 866.2F/g .

Example 8

The above power supply assembly is connected with the rotating barrel and the liquid inlet pipe to form a circuit, the inner wall of the rotating barrel is connected to the positive pole of the power supply, and the liquid inlet pipe is connected to the negative pole of the power supply. The above liquid storage tank is equipped with nickel nitrate solution with a concentration of 3.5mol/ ^dm3 and nickel acetate solution with a concentration of 1.0mol/dm3, and no nano-carbon material is added to the electrolyte. The calculation formula of the supergravity field strength generated by the electrodeposition is as follows: supergravity field strength=[(2πn/60) ² ×R/ g]g. Among them, n is 4230 rpm, R is 50mm, g is 9.8 m/s ² , and the supergravity field strength can be calculated as 1000g (g=9.8m·s ^-2 ). Turn on the DC power supply to output a current density of 500mA/cm ² to the inner wall of the rotating barrel, and conduct electrodeposition at a temperature of 90°C. Stop the machine after 1 hour of electrodeposition, scrape off, clean and dry the prepared electrodeposited product for later use. The electrodeposited product powder collected above is mixed with 9wt% acetylene black, pressed into sheets to make an electrode, and assembled into a supercapacitor with it, and the positive electrode is tested for capacity, and the specific capacity of the prepared manganese dioxide is 586.6F/g .

Claims (9)

1. A preparation method for supercapacitor and battery composite cathode material, characterized in that: (1) Preparation device There is a cylindrical shell-shaped rotary bucket in the upper part of the liquid storage tank. One end surface of the above-mentioned rotary bucket is provided with a reduced diameter, which is sealed and connected with the horizontal shaft of the motor outside the liquid storage tank. The other end surface of the rotary bucket is provided with a central through hole. , the central through hole is inserted with a horizontal liquid inlet pipe with an opening in the rotating barrel, the other end of the fixed liquid inlet pipe extends out of the liquid storage tank and connects with the liquid outlet of the circulation pump, the inlet of the circulation pump The liquid port is connected to the liquid outlet pipe at the bottom of the liquid storage tank, and a heating mechanism and a temperature display mechanism are arranged in the liquid storage tank, and a DC power supply or a pulse power supply is connected in series with an ammeter to form a power supply assembly; (2) Preparation method (1) Connect the power supply assembly with the rotating barrel and the liquid inlet pipe to form a circuit, the inner wall of the rotating barrel is connected to the positive pole of the power supply, and the liquid inlet pipe is connected to the negative pole of the power supply; (2) The above-mentioned liquid storage tank is equipped with an electrolyte solution, which is a soluble salt solution of divalent manganese ions. The concentration of the above-mentioned electrolyte solution is 0.05mol/dm ³ ~4.5mol/dm ³ , and 0-100g of /dm ³ carbon nanomaterials; (3) Turn on the DC or pulse power supply to output a current density of 0.5mA/cm ² to 500mA/cm ² on the inner wall of the rotating barrel, and conduct electrodeposition at a temperature of 15°C~90°C. The supergravity generated by the electrodeposition device The field strength is expressed in multiples of the gravitational field strength on the earth's surface, and the calculation formula is as follows: Supergravity field strength=[(2πn/60) ² ×R/ g]g, where n is the rotational speed of the rotating barrel per minute, and R is the inner wall of the rotating barrel Radius, g is the gravitational acceleration on the earth's surface of 9.8 m/s ² , adjust the rotation speed and diameter of the rotating barrel, and control the strength of the supergravity field within the range of 1g-1000g; (4) According to different electrodeposition conditions, the electrodeposition products formed by electrodeposition have different forms: a suspended in the electrolyte, the electrodeposition process can be carried out continuously, and the electrodeposition product can be collected through a filter device, cleaned and dried for later use; b Attached to the electrode on the inner wall of the rotating barrel, stop the machine after 1 to 5 hours of electrodeposition, scrape off the prepared composite material, clean it and dry it for later use; (5) Mix the electrodeposition product powder collected above with 5-15wt% acetylene black, and press it into a positive electrode of a supercapacitor or battery. 2. A preparation method for supercapacitor and battery composite cathode material, characterized in that: (1) Preparation device There is a cylindrical shell-shaped rotary bucket in the upper part of the liquid storage tank. One end surface of the above-mentioned rotary bucket is provided with a reduced diameter, which is sealed and connected with the horizontal shaft of the motor outside the liquid storage tank. The other end surface of the rotary bucket is provided with a central through hole. , the central through hole is inserted with a horizontal liquid inlet pipe with an opening in the rotating barrel, the other end of the fixed liquid inlet pipe extends out of the liquid storage tank and connects with the liquid outlet of the circulation pump, the inlet of the circulation pump The liquid port is connected to the liquid outlet pipe at the bottom of the liquid storage tank. There is a heating mechanism and a temperature display mechanism in the liquid storage tank. There is also a DC power supply or a pulse power supply connected in series with the ammeter, and the power supply assembly is connected to the rotary barrel and the liquid inlet pipe. make up a circuit; (2) Preparation method (1) Connect the power supply assembly with the rotating barrel and the liquid inlet pipe to form a circuit. The inner wall of the rotating barrel is connected to the negative pole of the power supply, and the liquid inlet pipe is connected to the positive pole of the power supply; (2) The above-mentioned storage tank is equipped with an electrolyte solution, which can be a soluble salt solution of divalent nickel ions. The concentration of the above-mentioned electrolyte solution is 0.05mol/dm ³ ~4.5mol/dm ³ . Add 0~ 100g/ ^dm3 nano-carbon material; (3) Turn on the DC or pulse power supply to output a current density of 0.5mA/cm ² to 500mA/cm ² on the inner wall of the rotating barrel, and conduct electrodeposition at a temperature of 15°C~90°C. The supergravity generated by the electrodeposition device The field strength is expressed in multiples of the gravitational field strength on the earth's surface, and the calculation formula is as follows: Supergravity field strength=[(2πn/60) ² ×R/ g]g, where n is the rotational speed of the rotating barrel per minute, and R is the inner wall of the rotating barrel Radius, g is the gravitational acceleration on the earth's surface of 9.8 m/s ² , adjust the rotation speed and diameter of the rotating barrel, and control the strength of the supergravity field within the range of 1g-1000g; (4) According to different electrodeposition conditions, the electrodeposition products formed by electrodeposition have different forms: a suspended in the electrolyte, the electrodeposition process can be carried out continuously, and the electrodeposition product can be collected through a filter device, cleaned and dried for later use; b Attached to the electrode on the inner wall of the rotating barrel, stop the machine after 1 to 5 hours of electrodeposition, scrape off the prepared composite material, clean it and dry it for later use; (5) Mix the electrodeposition product powder collected above with 5-15wt% acetylene black, and press it into a positive electrode of a supercapacitor or battery. 3. The method for preparing a supercapacitor and battery composite positive electrode material according to claim 1 or 2, characterized in that: a deflector is arranged in the above-mentioned rotating barrel. 4. The method for preparing a supercapacitor and battery composite anode material according to claim 3, characterized in that: the inner wall of the rotating barrel in contact with the electrolyte is coated with a platinum catalytic coating. 5. The method for preparing a supercapacitor and battery composite positive electrode material according to claim 4, characterized in that: a metal inner cylinder is arranged inside the rotating barrel. 6. The method for preparing a supercapacitor and battery composite positive electrode material according to claim 4, characterized in that: the rotating barrel is made of corrosion-resistant metal material. 7. The preparation method of supercapacitor and battery composite cathode material according to claim 1 or 2, characterized in that: said nano-carbon material can be carbon nanotubes, graphene, activated carbon, acetylene black, nano-graphite powder or carbon airgel. 8. the preparation method of supercapacitor and battery composite positive electrode material according to claim 1, is characterized in that: the salt solution of described divalent manganese ion refers to any one solution or two kinds of solutions in manganese sulfate, manganese acetate the mix of. 9. the preparation method of supercapacitor and battery composite cathode material according to claim 2, is characterized in that: the salt solution of described divalent nickel ion refers to nickel nitrate, nickel sulfate, nickel acetate, nickel sulfamate Any one solution or a mixture of multiple solutions.

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