CN111555654B - Integrated micro-nano energy recovery storage chip and working method thereof - Google Patents
Integrated micro-nano energy recovery storage chip and working method thereof Download PDFInfo
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- CN111555654B CN111555654B CN202010416009.6A CN202010416009A CN111555654B CN 111555654 B CN111555654 B CN 111555654B CN 202010416009 A CN202010416009 A CN 202010416009A CN 111555654 B CN111555654 B CN 111555654B
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- 238000011084 recovery Methods 0.000 title claims abstract description 25
- 238000003860 storage Methods 0.000 title claims abstract description 19
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- 238000010248 power generation Methods 0.000 claims abstract description 179
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 55
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- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02N—ELECTRIC MACHINES NOT OTHERWISE PROVIDED FOR
- H02N1/00—Electrostatic generators or motors using a solid moving electrostatic charge carrier
- H02N1/04—Friction generators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/005—Electrodes
- H01G4/008—Selection of materials
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- Manufacturing & Machinery (AREA)
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- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The integrated micro-nano energy recovery storage chip comprises a base, a middle layer, a top layer, a power generation positive electrode module, a power generation negative electrode module and a capacitor module which are nested in the three layers from bottom to top; the power generation positive electrode module and the power generation negative electrode module respectively generate positive and negative charges when the chip is vibrated, and the positive and negative charges are processed by the power management module and then are supplied to the outside; the capacitor module comprises a capacitor anode, a capacitor cathode and other component elements, and is used for storing electric energy converted from vibration energy when the generated power is larger than the power supply power and supplementing power outwards when the generated power is insufficient. The chip of the invention integrates the energy recovery and storage element, and can continuously supply power outwards and store surplus electric quantity. The capacitor anode and the capacitor cathode are made of high-density and high-porosity three-dimensional graphene, so that the capacitor is high in energy density, small in volume, and suitable for mobile consumer electronics, internet of things and the like.
Description
Technical Field
The invention relates to the technical field of energy recovery and storage, in particular to an integrated micro-nano energy recovery storage chip based on three-dimensional graphene and a working method thereof.
Background
Mobile consumer electronics and the internet of things are evolving rapidly, accompanied by mobile energy supply or distributed energy supply demands. Currently, mobile consumer electronics fields such as mobile phones, notebook computers, smart watches and the like mainly rely on battery power supply; the power supply of the nodes of the Internet of things adopts two modes of power grid and battery power supply. The problems of battery power supply include limited endurance time, limited battery charge and discharge times, easy performance degradation and the like; the power supply continuity of the power grid is strong, but a power supply network needs to be established, so that the complexity of the Internet of things and the construction and operation cost are additionally increased; in addition, for field operation Internet of things systems such as meteorological monitoring, geological monitoring and hydrologic monitoring, the power grid power supply cost is too high to be practical, and battery power supply is difficult to ensure long-time continuous power supply. Therefore, a mobile energy source capable of providing a continuous energy supply for a long time is of great importance for consumer electronics and internet of things development.
Disclosure of Invention
Aiming at the energy requirements of mobile consumer electronics and the Internet of things, the invention aims to provide an integrated micro-nano energy recovery storage chip capable of continuously supplying power for a long time and a working method thereof.
In order to achieve the above purpose, the present invention adopts the following scheme:
the integrated micro-nano energy recovery storage chip consists of a base 1, a middle layer 2, a top layer 3, a power generation positive electrode module 4, a power generation negative electrode module 5 and a capacitor module 6 which are nested in the three layers from bottom to top;
the base 1 is provided with an anode blind groove 1-1, a capacitor blind groove 1-2, a cathode blind groove 1-3, a base capacitor cathode lead hole 1-4 and a diaphragm step 1-5;
the middle layer 2 is provided with an anode through groove 2-1, a capacitor through groove 2-2, a cathode through groove 2-3 and a middle capacitor cathode lead hole 2-4; all through grooves of the middle layer 2 are of a structure penetrating through the upper surface and the lower surface;
the top layer 3 is provided with a power generation positive electrode lead hole 3-1, a power generation positive electrode collecting groove 3-2, a capacitor positive electrode lead hole 3-3, a capacitor positive electrode collecting groove 3-4, a top layer capacitor negative electrode lead hole 3-5, a power generation negative electrode collecting groove 3-6 and a power generation negative electrode lead hole 3-7; wherein each lead hole penetrates through the top layer 3, and each collecting groove is positioned on the lower surface of the top layer; the transverse position of each lead hole is positioned in the corresponding collecting groove area;
the base 1, the middle layer 2 and the top layer 3 are sequentially overlapped from bottom to top;
the positive blind groove 1-1, the positive through groove 2-1 and the power generation positive current collecting groove 3-2 have the same radial dimension, are mutually aligned and jointly enclose a cavity, and the power generation positive electrode 4-1 and the power generation positive current collector 4-2 are sequentially arranged in the cavity from bottom to top and are mutually contacted; the power generation positive electrode lead hole 3-1 is internally filled with a power generation positive electrode lead 4-3; a power generation positive electrode bonding pad 4-4 is arranged on the upper surface of the top layer 3 and positioned in the area around the end face of the power generation positive electrode lead hole 3-1; positive charges generated by the power generation positive electrode 4-1 are collected by the power generation positive electrode current collector 4-2 and are led out to the power generation positive electrode bonding pad 4-4 for storage through the power generation positive electrode lead 4-3; the power generation positive electrode 4-1, the power generation positive electrode current collector 4-2, the power generation positive electrode lead 4-3 and the power generation positive electrode bonding pad 4-4 form a power generation positive electrode module 4;
the radial dimensions of the cathode blind groove 1-3, the cathode through groove 2-3 and the power generation cathode current collecting groove 3-6 are the same, are mutually aligned, jointly enclose a cavity, and the power generation cathode 5-1 and the power generation cathode current collector 5-2 are sequentially arranged in the cavity from bottom to top and are mutually contacted; the power generation negative electrode lead 5-3 is filled in the power generation negative electrode lead hole 3-7; the upper surface of the top layer 3 is provided with a power generation negative electrode bonding pad 5-4 in the area around the end face of the power generation negative electrode lead hole 3-7; negative charges generated by the power generation negative electrode 5-1 are collected by the power generation negative electrode current collector 5-2 and are led out to the power generation negative electrode bonding pad 5-4 through the power generation negative electrode lead 5-3; the power generation negative electrode 5-1, the power generation negative electrode current collector 5-2, the power generation negative electrode lead 5-3 and the power generation negative electrode bonding pad 5-4 form a power generation negative electrode module 5;
the capacitor blind groove 1-2, the capacitor through groove 2-2 and the capacitor positive electrode current collecting groove 3-4 have the same radial dimension and are mutually aligned to form a cavity together, and a capacitor negative electrode current collector 6-5, a capacitor negative electrode 6-3, a diaphragm 6-2, a capacitor positive electrode 6-1 and a capacitor positive electrode current collector 6-4 are sequentially arranged in the cavity from bottom to top; the radial dimension of the diaphragm 6-2 is larger than that of the capacitor anode 6-1 and the capacitor cathode 6-3, and the exceeding part is embedded in a radial shallow groove formed by the diaphragm step 1-5 and the lower surface of the middle layer 2; the capacitor anode lead hole 3-3 is internally filled with a capacitor anode lead 6-6; the upper surface of the top layer 3 and the area around the end face of the capacitor anode lead hole 3-3 are provided with capacitor anode bonding pads 6-8; the base capacitor negative electrode lead hole 1-4, the middle capacitor negative electrode lead hole 2-4 and the top capacitor negative electrode lead hole 3-5 have the same diameter, the axes are coincident, a complete through hole is formed by sequentially communicating from bottom to top, and the capacitor negative electrode lead 6-7 is filled in the through hole; the upper surface of the top layer 3 and the area around the end face of the capacitor negative electrode lead 6-7 are provided with capacitor negative electrode bonding pads 6-9; the capacitor anode 6-1, the diaphragm 6-2, the capacitor cathode 6-3, the capacitor anode current collector 6-4, the capacitor cathode current collector 6-5, the capacitor anode lead 6-6, the capacitor cathode lead 6-7, the capacitor anode bonding pad 6-8 and the capacitor cathode bonding pad 6-9 form a capacitor module 6; the capacitor anode 6-1 is contacted with the capacitor anode current collector 6-4 and is connected with the capacitor anode bonding pad 6-8 through the capacitor anode lead 6-6; positive charge is introduced into the capacitive anode 6-1 along the capacitive anode lead 6-6 and the capacitive anode current collector 6-4 from the anode pad 6-8; the capacitor negative electrode 6-3 is in contact with the capacitor negative electrode current collector 6-5 and is connected with the capacitor negative electrode bonding pad 6-9 through the capacitor negative electrode lead 6-7; negative charge is introduced from the capacitor negative electrode bonding pad 6-9 along the capacitor negative electrode lead 6-7 and the capacitor negative electrode current collector 6-5 into the capacitor negative electrode 6-3;
the preparation method of the capacitor anode 6-1 and the capacitor cathode 6-3 comprises the following steps:
preparation of a three-dimensional frame: using a 3D foam nickel bracket as a template, and growing a graphene film on the surface of the 3D foam nickel bracket by CVD to form a three-dimensional frame;
preparation of graphene oxide polystyrene microsphere GO/PS dispersion liquid: graphene oxide prepared by a modified Hummers method, negatively charged; amination of polystyrene microspheres is carried out through nitration and reduction, so as to prepare positively charged aminated polystyrene microspheres; placing graphene oxide and an aminated polystyrene microsphere into deionized water for fully stirring, wherein the graphene oxide and the aminated polystyrene microsphere are respectively negatively charged and positively charged, and the positive charge and the negative charge are mutually attracted, so that the graphene oxide is wrapped on the surface of the aminated polystyrene microsphere to form GO/PS dispersion liquid;
and (III) filling graphene oxide polystyrene microspheres: soaking the three-dimensional frame obtained in the step (I) in the GO/PS dispersion liquid to ensure that the GO/PS is fully contacted with the three-dimensional frame; then drying the GO/PS filled three-dimensional frame in an oven at 400-600 ℃;
(IV) repeating the step (III) to ensure that the GO/PS is fully filled into the holes of the three-dimensional framework and reaches the required thickness;
and (V) removing the polystyrene microspheres: placing the three-dimensional frame filled with GO/PS in a single-channel tube furnace, heating at constant temperature in an argon atmosphere at 400-600 ℃ to remove polystyrene microspheres;
and (six) removing foam nickel: putting the three-dimensional structure obtained in the step (five) into nickel corrosive liquid, dissolving and removing the foam nickel bracket to obtain three-dimensional graphene oxide, and cleaning the three-dimensional graphene oxide to remove residual organic matters and metal ions;
and (seventh) drying: heating and drying the obtained three-dimensional graphene oxide;
(eight) reduction: reducing the obtained three-dimensional graphene oxide to obtain three-dimensional graphene;
and (nine) cutting: and cutting the three-dimensional graphene according to the design sizes of the capacitor anode 6-1 and the capacitor cathode 6-3 to obtain the required capacitor anode 6-1 and the capacitor cathode 6-3.
The structure of the power generation positive electrode 4-1 is a positive electrode porous three-dimensional structure 4-1-2 internally containing positive particles 4-1-1.
The material of the positive electrode porous three-dimensional structure 4-1-2 in the power generation positive electrode 4-1 is three-dimensional graphene with high porosity, the material of the positive electrode particles 4-1-1 is substance particles with work functions larger than that of the graphene, and the substance particles comprise particles of one or more materials of gold, copper and carbon.
The structure of the power generation anode 5-1 is an anode porous three-dimensional structure 5-1-2 containing negative particles 5-1-1.
The material of the negative electrode porous three-dimensional structure 5-1-2 in the power generation negative electrode 5-1 is three-dimensional graphene with high porosity, the material of the negative electrode particles 5-1-1 is substance particles with work functions smaller than that of the graphene, and the substance particles comprise particles of one or more materials of monocrystalline silicon, silicon oxide, silver, lead and calcium.
The base 1, the middle layer 2 and the top layer 3 are made of inorganic materials or organic polymer materials; or organic polymer materials such as polydimethylsiloxane, polymethyl methacrylate, and the like. The resistivity of the base 1, the middle layer 2 and the top layer 3 is more than 1000 omega cm; the material of each lead and pad is a metal having good conductivity.
The inorganic material is monocrystalline silicon, polycrystalline silicon, amorphous silicon, silicon oxide or silicon nitride; the organic polymer material is polydimethylsiloxane or polymethyl methacrylate; the metal with good conductivity is copper, gold, aluminum, chromium, nickel or titanium.
The cross sections of the power generation positive electrode module 4, the power generation negative electrode module 5 and the capacitor module 6 are round or rectangular; the relative positions of the three are determined according to specific requirements, and the capacitor module 6 is positioned in the middle or at one side of the power generation positive electrode module 4 and the power generation negative electrode module 5.
The working principle of the integrated micro-nano energy recovery storage chip is as follows:
the chip is internally provided with a power generation positive electrode 4-1 and a power generation negative electrode 5-1, when the chip is subjected to external vibration, positive particles 4-1-1 shake randomly and collide and rub with the wall surface of a positive electrode porous three-dimensional structure 4-1-2, positive charges are generated in the collision and rubbing process due to different materials and different work functions, the positive charges are collected through a power generation positive electrode current collector 4-2, and the positive charges are led out to a power generation positive electrode bonding pad 4-4 through a power generation positive electrode lead 4-3; meanwhile, negative particles 5-1-1 and a negative porous three-dimensional structure 5-1-2 are subjected to collision friction, the materials of the negative particles and the negative porous three-dimensional structure are different, the work functions of the negative particles and the negative porous structure are different, negative charges are generated in the collision friction process, are collected through a power generation negative current collector 5-2, and are led out to a power generation negative bonding pad 5-4 through a power generation negative lead 5-3; thereby, the power generation positive electrode pad 4-4 and the power generation negative electrode pad 5-4 respectively provide positive electricity and negative electricity to the outside; the power supply voltage is not stable enough, is processed by a peripheral voltage stabilizing rectifying circuit, and is converted into a power supply with stable output by a power supply management module.
The capacitor module 6 is used for storing electric energy; when the generated power is larger than the power required by a load or external power supply is not needed, positive and negative charges output by the positive power generation module 4 and the negative power generation module 5 are respectively led into the positive capacitor electrode 6-1 and the negative capacitor electrode 6-3 of the capacitor module 6 for storage after passing through the power management module; when the generated power is smaller than the load power, the electric energy stored by the capacitor module 6 is output outwards to supplement the generated power.
Compared with the prior art, the invention has the following advantages:
1) The chip can continuously convert vibration energy in the environment into electric energy, and continuous movable energy supply is realized.
2) The power generation positive electrode module and the power generation negative electrode module respectively contain porous three-dimensional graphene and corresponding positive and negative particles, when the chip is vibrated, the particles collide and rub with the wall surface of the three-dimensional graphene to respectively generate positive and negative charges, and the positive charges and the negative charges are processed by the power management module to be externally supplied; the capacitor module stores electric energy converted from vibration energy when the generated power is larger than the power supply power, supplements power supply outwards when the generated power is insufficient, integrates an energy recovery element and an energy storage element in one chip, and realizes energy storage when the power supply gap outwards or the load power is smaller than the generated power.
3) The micro-nano device is designed and manufactured, the chip size is small, the energy density is high, and the micro-nano device is suitable for mobile energy supply requirements of mobile consumer electronic products, the Internet of things and the like; and the method can be used for mass production, has low cost and high production efficiency, and is suitable for large-scale application.
4) The three-dimensional graphene is adopted as the anode and the cathode of the capacitor module, so that the energy storage density is high, the efficiency is high, and the chip volume and the weight are greatly reduced. And the manufacturing method of the anode and the cathode of the capacitor module is efficient and feasible, and is suitable for popularization.
Drawings
FIG. 1 is a block diagram of an integrated micro-nano energy recovery memory chip of the present invention.
Fig. 2 is a schematic view of a base structure.
Fig. 3 is a schematic diagram of an intermediate layer structure.
Fig. 4 is a schematic top layer structure.
FIG. 5 is a schematic diagram of the power generation anode in whole and in part.
Fig. 6 is a schematic diagram of the whole and part of the power generation negative electrode.
FIG. 7 is a schematic diagram of the operation of an integrated micro-nano energy recovery memory chip.
Detailed Description
The specific embodiments of the integrated micro-nano energy recovery memory chip of the invention are further described with reference to the accompanying drawings.
With reference to fig. 1, fig. 2, fig. 3 and fig. 4, the present invention aims at providing an integrated micro-nano energy recovery storage chip capable of continuously supplying power for a long time, aiming at energy demands of mobile consumer electronics and internet of things. In order to achieve the purpose, the integrated micro-nano energy recovery storage chip is composed of a base 1, a middle layer 2, a top layer 3, a power generation positive electrode module 4, a power generation negative electrode module 5 and a capacitor module 6 which are nested in the three layers from bottom to top.
The base 1 is provided with an anode blind groove 1-1, a capacitor blind groove 1-2, a cathode blind groove 1-3, a base capacitor cathode lead hole 1-4 and a diaphragm step 1-5.
The middle layer 2 is provided with an anode through groove 2-1, a capacitor through groove 2-2, a cathode through groove 2-3 and a middle capacitor cathode lead hole 2-4. All through grooves of the middle layer are of a structure penetrating through the upper surface and the lower surface.
The top layer 3 is provided with a power generation positive electrode lead hole 3-1, a power generation positive electrode collecting groove 3-2, a capacitor positive electrode lead hole 3-3, a capacitor positive electrode collecting groove 3-4, a top layer capacitor negative electrode lead hole 3-5, a power generation negative electrode collecting groove 3-6 and a power generation negative electrode lead hole 3-7. Wherein each lead hole penetrates through the top layer, and each collecting groove is positioned on the lower surface of the top layer; each lead hole is located laterally within a corresponding current collector region.
The base 1, the middle layer 2 and the top layer 3 are sequentially overlapped from bottom to top.
The positive blind groove 1-1, the positive through groove 2-1 and the power generation positive current collecting groove 3-2 have the same radial dimension, are mutually aligned and jointly enclose a cavity, and the power generation positive electrode 4-1 and the power generation positive current collector 4-2 are sequentially arranged in the cavity from bottom to top and are mutually contacted. The power generation positive electrode lead hole 3-1 is internally filled with a power generation positive electrode lead 4-3; and a power generation positive electrode bonding pad 4-4 is arranged on the upper surface of the top layer 3 and positioned in the area around the end face of the power generation positive electrode lead hole 3-1. Positive charges generated by the power generation positive electrode 4-1 can be collected by the power generation positive electrode current collector 4-2 and led out to the power generation positive electrode bonding pad 4-4 for storage through the power generation positive electrode lead 4-3. The power generation positive electrode 4-1, the power generation positive electrode current collector 4-2, the power generation positive electrode lead 4-3 and the power generation positive electrode bonding pad 4-4 form a power generation positive electrode module 4.
The cathode blind groove 1-3, the cathode through groove 2-3 and the power generation cathode current collecting groove 3-6 have the same radial dimension, are mutually aligned and jointly enclose a cavity, and the power generation cathode 5-1 and the power generation cathode current collector 5-2 are sequentially arranged in the cavity from bottom to top and are mutually contacted. The power generation negative electrode lead 5-3 is filled in the power generation negative electrode lead hole 3-7; and a power generation negative electrode bonding pad 5-4 is arranged on the upper surface of the top layer 3 and positioned at the area around the end face of the power generation negative electrode lead hole 3-7. Negative charge generated by the negative power generation electrode 5-1 can be collected by the negative power generation electrode current collector 5-2 and conducted to the negative power generation electrode pad 5-4 through the negative power generation electrode lead 5-3 for storage. The power generation negative electrode 5-1, the power generation negative electrode current collector 5-2, the power generation negative electrode lead 5-3 and the power generation negative electrode bonding pad 5-4 form a power generation negative electrode module 5.
The capacitor blind groove 1-2, the capacitor through groove 2-2 and the capacitor positive electrode current collecting groove 3-4 have the same radial dimension and are mutually aligned to form a cavity together, and the capacitor negative electrode current collector 6-5, the capacitor negative electrode 6-3, the diaphragm 6-2, the capacitor positive electrode 6-1 and the capacitor positive electrode current collector 6-4 are sequentially arranged in the cavity from bottom to top. The radial dimension of the diaphragm 6-2 is larger than that of the capacitor anode 6-1 and the capacitor cathode 6-3, and the exceeding part is embedded in a radial shallow groove formed by the diaphragm step 1-5 and the lower surface of the middle layer 2. The capacitor anode lead hole 3-3 is internally filled with a capacitor anode lead 6-6. The upper surface of the top layer 3 and the area around the end face of the capacitor anode lead hole 3-3 are provided with capacitor anode bonding pads 6-8. The base capacitor negative electrode lead hole 1-4, the middle capacitor negative electrode lead hole 2-4 and the top capacitor negative electrode lead hole 3-5 have the same diameter, the axes are coincident, the whole through holes are formed by sequentially communicating from bottom to top, and the capacitor negative electrode lead 6-7 is filled in the inside. The upper surface of the top layer 3 and the area around the end face of the capacitor negative electrode lead 6-7 are provided with capacitor negative electrode pads 6-9. The capacitor anode 6-1, the diaphragm 6-2, the capacitor cathode 6-3, the capacitor anode current collector 6-4, the capacitor cathode current collector 6-5, the capacitor anode lead 6-6, the capacitor cathode lead 6-7, the capacitor anode bonding pad 6-8 and the capacitor cathode bonding pad 6-9 form a capacitor module 6. The capacitor anode 6-1 is contacted with the capacitor anode current collector 6-4 and is connected with the capacitor anode bonding pad 6-8 through the capacitor anode lead 6-6; positive charge may be directed from the positive electrode pad 6-8 along the capacitor positive electrode lead 6-6 and the capacitor positive electrode current collector 6-4 to the capacitor positive electrode 6-1. The capacitor negative electrode 6-3 is in contact with the capacitor negative electrode current collector 6-5 and is connected with the capacitor negative electrode bonding pad 6-9 through the capacitor negative electrode lead 6-7; negative charge may be directed from the capacitor negative electrode pad 6-9 along the capacitor negative electrode lead 6-7 and the capacitor negative electrode current collector 6-5 to the capacitor negative electrode 6-3.
As shown in FIG. 5, the structure of the positive electrode 4-1 for power generation is a positive electrode porous three-dimensional structure 4-1-2 containing positive particles 4-1-1 inside. When the chip is subjected to external vibration, the positive particles 4-1-1 shake randomly and collide and rub with the wall surface of the positive porous three-dimensional structure 4-1-2, and positive charges are generated in the collision and rubbing process because the positive particles and the positive particles are made of different materials and have different work functions.
As shown in FIG. 6, the structure of the negative electrode 5-1 for power generation is a negative electrode porous three-dimensional structure 5-1-2 containing negative particles 5-1-1 inside. When the chip is subjected to external vibration, negative particles 5-1-1 and the negative porous three-dimensional structure 5-1-2 are subjected to collision friction, the materials of the negative particles and the negative porous three-dimensional structure are different, the work functions of the negative particles are different, and negative charges are generated in the collision friction process.
As shown in fig. 7, the working principle of the integrated micro-nano energy recovery storage chip of the invention is as follows:
the chip is internally provided with a power generation positive electrode 4-1 and a power generation negative electrode 5-1, positive particles 4-1-1 randomly shake when the chip is subjected to external vibration, collide and rub with the wall surface of the positive electrode porous three-dimensional structure 4-1-2, and positive charges are generated in the collision and rubbing processes due to different materials and different work functions, are collected through the power generation positive electrode current collector 4-2 and are guided out to the power generation positive electrode bonding pad 4-4 through the power generation positive electrode lead 4-3. Meanwhile, negative particles 5-1-1 and the negative porous three-dimensional structure 5-1-2 are subjected to collision friction, materials of the negative particles and the negative porous three-dimensional structure are different, work functions of the negative particles and the negative porous structure are different, negative charges are generated in the collision friction process, are collected through the power generation negative current collector 5-2, and are guided out to the power generation negative bonding pad 5-4 through the power generation negative lead 5-3. Thus, the power generation positive electrode pad 4-4 and the power generation negative electrode pad 5-4 can respectively provide positive electricity and negative electricity to the outside; the power supply voltage is not stable enough, is processed by a peripheral voltage stabilizing rectifying circuit, and is converted into a power supply with stable output by a power supply management module.
The function of the capacitive module 6 is to store electrical energy. When the generated power is larger than the power required by the load or the power is not required to be supplied to the outside, positive and negative charges output by the positive power generation module 4 and the negative power generation module 5 are respectively led into the positive capacitor electrode 6-1 and the negative capacitor electrode 6-3 of the capacitor module 6 for storage after passing through the power management module. The electric energy stored in the capacitor module 6 can be output to the outside for power supplement when the generated power is smaller than the load power.
The invention relates to a specific preparation method of a capacitor anode 6-1 and a capacitor cathode 6-3, which comprises the following steps:
and (one) preparing a three-dimensional framework. Using a 3D foam nickel bracket as a template, and growing a graphene film on the surface of the 3D foam nickel bracket by CVD to form a three-dimensional frame;
preparation of graphene oxide polystyrene microsphere (GO/PS) dispersion liquid. Graphene oxide prepared by the modified Hummers method is negatively charged. The polystyrene microsphere is aminated through nitration and reduction to prepare the positively charged aminated polystyrene microsphere. Placing graphene oxide and aminated polystyrene microspheres into deionized water for fully stirring, wherein the graphene oxide and the aminated polystyrene microspheres are respectively negatively charged and positively charged, the positive charge and the negative charge are mutually attracted, and the graphene oxide can be wrapped on the surfaces of the polystyrene microspheres to form GO/PS dispersion liquid;
and (III) filling graphene oxide polystyrene microspheres. Immersing the three-dimensional frame obtained in the step (-) in the GO/PS solution to ensure that the GO/PS is fully contacted with the three-dimensional frame. Then drying the GO/PS filled three-dimensional frame in an oven at 500 ℃;
and (IV) repeating the step (III) five times to ensure that the GO/PS is fully filled into the holes of the three-dimensional framework, wherein the thickness of the graphene layer is 20nm.
And (V) removing the polystyrene microspheres. Placing the three-dimensional framework attached with GO/PS in a single-channel tube furnace, heating at constant temperature in argon atmosphere at 500 ℃ to remove polystyrene microspheres;
and (sixth) removing foam nickel. Putting the three-dimensional structure obtained in the step (five) into nickel corrosive liquid, dissolving and removing the foam nickel bracket to obtain three-dimensional graphene oxide, and cleaning the three-dimensional graphene oxide to remove residual organic matters and metal ions;
and (seventh) drying. Heating and drying the obtained three-dimensional graphene oxide;
and (eight) reduction. Reducing the obtained three-dimensional graphene oxide to obtain three-dimensional graphene;
and (nine) cutting. And cutting the three-dimensional graphene according to the design dimensions of the capacitor anode 6-1 and the capacitor cathode 6-3 to obtain the capacitor anode 6-1 with the diameter of 1000 microns and the thickness of 150 microns and the capacitor cathode 6-3 with the diameter of 1000 microns and the thickness of 150 microns.
Claims (9)
1. The integrated micro-nano energy recovery storage chip is characterized in that: the power generation device comprises a base (1), a middle layer (2), a top layer (3), a power generation positive electrode module (4), a power generation negative electrode module (5) and a capacitor module (6), wherein the power generation positive electrode module (4), the power generation negative electrode module (5) and the capacitor module are nested in the three layers of structures from bottom to top;
the base (1) is provided with an anode blind groove (1-1), a capacitor blind groove (1-2) and a cathode blind groove (1-3), a base capacitor cathode lead hole (1-4) and a diaphragm step (1-5);
the middle layer (2) is provided with an anode through groove (2-1), a capacitor through groove (2-2), a cathode through groove (2-3) and a middle capacitor cathode lead hole (2-4); all through grooves of the middle layer (2) are of a structure penetrating through the upper surface and the lower surface;
the top layer (3) is provided with a power generation positive electrode lead hole (3-1), a power generation positive electrode collecting groove (3-2), a capacitor positive electrode lead hole (3-3), a capacitor positive electrode collecting groove (3-4), a top layer capacitor negative electrode lead hole (3-5), a power generation negative electrode collecting groove (3-6) and a power generation negative electrode lead hole (3-7); wherein each lead hole penetrates through the top layer (3), and each collecting groove is positioned on the lower surface of the top layer; the transverse position of each lead hole is positioned in the corresponding collecting groove area;
the base (1), the middle layer (2) and the top layer (3) are sequentially overlapped from bottom to top;
the positive blind groove (1-1), the positive through groove (2-1) and the power generation positive current collecting groove (3-2) have the same radial dimension, are mutually aligned and jointly enclose a cavity, and the power generation positive electrode (4-1) and the power generation positive current collector (4-2) are sequentially arranged in the cavity from bottom to top and are mutually contacted; the inside of the power generation positive electrode lead hole (3-1) is filled with a power generation positive electrode lead (4-3); a power generation positive electrode bonding pad (4-4) is arranged on the upper surface of the top layer (3) and positioned in the area around the end face of the power generation positive electrode lead hole (3-1); positive charges generated by the power generation positive electrode (4-1) are collected by the power generation positive electrode current collector (4-2) and are led out to the power generation positive electrode bonding pad (4-4) through the power generation positive electrode lead (4-3); the power generation positive electrode (4-1), the power generation positive electrode current collector (4-2), the power generation positive electrode lead (4-3) and the power generation positive electrode bonding pad (4-4) form a power generation positive electrode module (4);
the cathode blind grooves (1-3), the cathode through grooves (2-3) and the power generation cathode current collecting grooves (3-6) have the same radial dimension, are mutually aligned and jointly enclose a cavity, and the power generation cathode (5-1) and the power generation cathode current collector (5-2) are sequentially arranged in the cavity from bottom to top and are mutually contacted; the power generation negative electrode lead hole (3-7) is internally filled with a power generation negative electrode lead (5-3); a power generation negative electrode bonding pad (5-4) is arranged on the upper surface of the top layer (3) and positioned in the area around the end face of the power generation negative electrode lead hole (3-7); negative charges generated by the power generation negative electrode (5-1) are collected by a power generation negative electrode current collector (5-2) and are led out to a power generation negative electrode bonding pad (5-4) through a power generation negative electrode lead (5-3); the power generation negative electrode (5-1), the power generation negative electrode current collector (5-2), the power generation negative electrode lead (5-3) and the power generation negative electrode bonding pad (5-4) form a power generation negative electrode module (5);
the capacitor blind groove (1-2), the capacitor through groove (2-2) and the capacitor positive electrode current collecting groove (3-4) have the same radial dimension and are mutually aligned to form a cavity together, and a capacitor negative electrode current collector (6-5), a capacitor negative electrode (6-3), a diaphragm (6-2), a capacitor positive electrode (6-1) and a capacitor positive electrode current collector (6-4) are sequentially arranged in the cavity from bottom to top; the radial dimension of the diaphragm (6-2) is larger than that of the capacitor anode (6-1) and the capacitor cathode (6-3), and the exceeding part is embedded in a radial shallow groove formed by the diaphragm step (1-5) and the lower surface of the middle layer (2); the capacitor anode lead hole (3-3) is internally filled with a capacitor anode lead (6-6); a capacitor positive electrode bonding pad (6-8) is arranged on the upper surface of the top layer (3) and positioned in the area around the end face of the capacitor positive electrode lead hole (3-3); the base capacitor negative electrode lead hole (1-4), the middle capacitor negative electrode lead hole (2-4) and the top capacitor negative electrode lead hole (3-5) have the same diameter, the axes are overlapped, a complete through hole is formed by sequentially communicating from bottom to top, and the capacitor negative electrode lead (6-7) is filled in the through hole; the upper surface of the top layer (3) and the area around the end face of the capacitor negative electrode lead (6-7) are provided with capacitor negative electrode bonding pads (6-9); the capacitor positive electrode (6-1), the diaphragm (6-2), the capacitor negative electrode (6-3), the capacitor positive electrode current collector (6-4), the capacitor negative electrode current collector (6-5), the capacitor positive electrode lead (6-6), the capacitor negative electrode lead (6-7), the capacitor positive electrode bonding pad (6-8) and the capacitor negative electrode bonding pad (6-9) form a capacitor module (6); the capacitor anode (6-1) is contacted with the capacitor anode current collector (6-4) and is connected with the capacitor anode bonding pad (6-8) through the capacitor anode lead (6-6); positive charge is introduced into the capacitive anode (6-1) from the anode pad (6-8) along the capacitive anode lead (6-6) and the capacitive anode current collector (6-4); the capacitor negative electrode (6-3) is in contact with the capacitor negative electrode current collector (6-5) and is connected with the capacitor negative electrode bonding pad (6-9) through the capacitor negative electrode lead (6-7); negative charge is introduced into the capacitor cathode (6-3) from the capacitor cathode bonding pad (6-9) along the capacitor cathode lead (6-7) and the capacitor cathode current collector (6-5);
the preparation method of the capacitor anode (6-1) and the capacitor cathode (6-3) comprises the following steps:
preparation of a three-dimensional frame: using a 3D foam nickel bracket as a template, and growing a graphene film on the surface of the 3D foam nickel bracket by CVD to form a three-dimensional frame;
preparation of graphene oxide polystyrene microsphere GO/PS dispersion liquid: graphene oxide prepared by a modified Hummers method, negatively charged; amination of polystyrene microspheres is carried out through nitration and reduction, so as to prepare positively charged aminated polystyrene microspheres; placing graphene oxide and an aminated polystyrene microsphere into deionized water for fully stirring, wherein the graphene oxide and the aminated polystyrene microsphere are respectively negatively charged and positively charged, and the positive charge and the negative charge are mutually attracted, so that the graphene oxide is wrapped on the surface of the aminated polystyrene microsphere to form GO/PS dispersion liquid;
and (III) filling graphene oxide polystyrene microspheres: soaking the three-dimensional frame obtained in the step (I) in the GO/PS dispersion liquid to ensure that the GO/PS is fully contacted with the three-dimensional frame; then drying the GO/PS filled three-dimensional frame in an oven at 400-600 ℃;
(IV) repeating the step (III) to ensure that the GO/PS is fully filled into the holes of the three-dimensional framework and reaches the required thickness;
and (V) removing the polystyrene microspheres: placing the three-dimensional frame filled with GO/PS in a single-channel tube furnace, heating at constant temperature in an argon atmosphere at 400-600 ℃ to remove polystyrene microspheres;
and (six) removing foam nickel: putting the three-dimensional structure obtained in the step (five) into nickel corrosive liquid, dissolving and removing the foam nickel bracket to obtain three-dimensional graphene oxide, and cleaning the three-dimensional graphene oxide to remove residual organic matters and metal ions;
and (seventh) drying: heating and drying the obtained three-dimensional graphene oxide;
(eight) reduction: reducing the obtained three-dimensional graphene oxide to obtain three-dimensional graphene;
and (nine) cutting: and cutting the three-dimensional graphene according to the design sizes of the capacitor anode (6-1) and the capacitor cathode (6-3) to obtain the required capacitor anode (6-1) and the capacitor cathode (6-3).
2. The integrated micro-nano energy recovery memory chip of claim 1, wherein: the structure of the power generation positive electrode (4-1) is a positive electrode porous three-dimensional structure (4-1-2) internally containing positive particles (4-1-1).
3. The integrated micro-nano energy recovery memory chip of claim 2, wherein: the material of the positive electrode porous three-dimensional structure (4-1-2) in the power generation positive electrode (4-1) is three-dimensional graphene with high porosity, the material of the positive electrode particles (4-1-1) is substance particles with work functions larger than that of the graphene, and the substance particles comprise particles of one or more materials of gold, copper and carbon.
4. The integrated micro-nano energy recovery memory chip of claim 1, wherein: the structure of the power generation negative electrode (5-1) is a negative electrode porous three-dimensional structure (5-1-2) containing negative particles (5-1-1) inside.
5. The integrated micro-nano energy recovery memory chip of claim 4, wherein: the material of the negative electrode porous three-dimensional structure (5-1-2) in the power generation negative electrode (5-1) is three-dimensional graphene with high porosity, the material of the negative electrode particles (5-1-1) is substance particles with work functions smaller than that of graphene, and the substance particles comprise particles of one or more materials of monocrystalline silicon, silicon oxide, silver, lead and calcium.
6. The integrated micro-nano energy recovery memory chip of claim 1, wherein: the base (1), the middle layer (2) and the top layer (3) are made of inorganic materials or organic polymer materials; the resistivity of the base (1), the middle layer (2) and the top layer (3) is more than 1000 omega cm;
the material of each lead and pad is a metal having good conductivity.
7. The integrated micro-nano energy recovery memory chip of claim 6, wherein: the inorganic material is monocrystalline silicon, polycrystalline silicon, amorphous silicon, silicon oxide or silicon nitride; the organic polymer material is polydimethylsiloxane or polymethyl methacrylate; the metal with good conductivity is copper, gold, aluminum, chromium, nickel or titanium.
8. The integrated micro-nano energy recovery memory chip of claim 1, wherein: the cross sections of the power generation positive electrode module (4), the power generation negative electrode module (5) and the capacitor module (6) are round or rectangular; the relative positions of the three are determined according to specific requirements, and the capacitor module (6) is positioned in the middle or at one side of the power generation positive electrode module (4) and the power generation negative electrode module (5).
9. The method for operating an integrated micro-nano energy recovery memory chip of any one of claims 1 to 8, wherein: the chip is internally provided with a power generation positive electrode (4-1) and a power generation negative electrode (5-1), positive particles (4-1-1) randomly shake when the chip is subjected to external vibration, collide and rub with the wall surface of the positive electrode porous three-dimensional structure (4-1-2), and because the positive particles and the positive particles are made of different materials and have different work functions, positive charges are generated in the collision and rubbing processes and are collected through a power generation positive electrode current collector (4-2), and are led out to a power generation positive electrode bonding pad (4-4) through a power generation positive electrode lead (4-3); meanwhile, negative particles (5-1-1) and a negative porous three-dimensional structure (5-1-2) generate collision friction, materials of the negative particles and the negative porous three-dimensional structure are different, work functions of the negative particles and the negative porous structure are different, negative charges are generated in the collision friction process, the negative charges are collected through a power generation negative current collector (5-2), and the negative particles are led out to a power generation negative electrode bonding pad (5-4) through a power generation negative electrode lead (5-3); thereby, the positive power generation electrode pad (4-4) and the negative power generation electrode pad (5-4) respectively provide positive electricity and negative electricity to the outside; the power supply voltage is not stable enough, is required to be processed by a peripheral voltage stabilizing and rectifying circuit, and is converted into a power supply with stable output through a power supply management module;
the capacitor module (6) is used for storing electric energy; when the generated power is larger than the power required by a load or power is not required to be supplied to the outside, positive and negative charges output by the positive power generation module (4) and the negative power generation module (5) are respectively led into a positive capacitor electrode (6-1) and a negative capacitor electrode (6-3) of the capacitor module (6) for storage after passing through the power management module; and when the generated power is smaller than the load power, the electric energy stored by the capacitor module (6) is output outwards to supplement the generated power.
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