CN112447945B - 3D graphene based carbon-nickel hydride battery and preparation method thereof - Google Patents

3D graphene based carbon-nickel hydride battery and preparation method thereof Download PDF

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CN112447945B
CN112447945B CN201910830138.7A CN201910830138A CN112447945B CN 112447945 B CN112447945 B CN 112447945B CN 201910830138 A CN201910830138 A CN 201910830138A CN 112447945 B CN112447945 B CN 112447945B
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electrode
graphene
carbon
battery
nickel
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CN112447945A (en
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王坚
金叶
沈浩
焦昌梅
黄兵
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Yancheng Teachers University
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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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/24—Alkaline accumulators
    • H01M10/28—Construction or manufacture
    • H01M10/286—Cells or batteries with wound or folded electrodes
    • 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
    • H01M4/24—Electrodes for alkaline 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
    • H01M4/24—Electrodes for alkaline accumulators
    • H01M4/26—Processes of manufacture
    • H01M4/28—Precipitating active material on the carrier
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention relates to a 3D graphene based carbon-nickel hydrogen battery and a preparation method thereof, wherein the preparation method comprises the steps of taking graphite paper and a carbon-containing conductive adhesive as raw materials, coating a layer of the carbon-containing conductive adhesive on one surface of the graphite paper, drying and curing to form an electrode material compounded by the graphite paper and the carbon-containing conductive adhesive layer; the other side of the graphite paper is divided into a polar lug area, a battery reaction area and the rest part serving as a third area, and the third area is coated with hydrophobic glue for sealing and curing; performing graphene treatment on the battery reaction zone to prepare a graphene carbon anode; the prepared graphene carbon electrode is used as a positive electrode, hydrogen storage alloy powder and hydroxyl nickel powder are mixed and pressed on a foam nickel sheet to form a battery negative electrode, a polypropylene film is used as a diaphragm, and potassium hydroxide solution is used as electrolyte, so that the 3D graphene carbon-nickel hydrogen full battery is assembled. The invention can produce carbon-nickel-hydrogen battery with high specific energy; the raw materials have wide sources, the cost is low, and the preparation method is simple and environment-friendly; the product performance is stable and controllable, and the method is suitable for industrial production.

Description

3D graphene based carbon-nickel hydride battery and preparation method thereof
Technical Field
The invention relates to the technical field of application of graphene carbon materials to batteries or capacitive chemical energy storage, in particular to a 3D graphene carbon-nickel-hydrogen battery and a preparation method thereof.
Background
Graphene (Graphene) is an allotrope of carbon elements newly recognized by human beings, following fullerene and carbon nanotubes. Graphene is a carbon atom represented by sp2Hybrid orbitals form bonds, and the carbon material has a single-layer two-dimensional honeycomb lattice structure formed by a six-membered ring structure. The unique structure of the graphene brings a series of new to the grapheneThe graphene material has special properties such as colorlessness and transparency (the absorbed light intensity is only 2.3%), high conductivity (the conductivity of single-layer graphene is similar to that of copper), excellent mechanical properties (the tensile strength can reach 50-200 GPa, the elastic modulus can reach 1TPa, the tensile strength of the single-layer graphene is 100 times that of a steel sheet with the same thickness), and an ultra-large specific surface area (more than 300 million graphene exists in graphite particles with the thickness of 1 mm). Due to the characteristics, the graphene has wide application prospects in the energy storage fields of super capacitors, chemical batteries and the like. However, the graphene is directly used in the production practice in the energy storage field, and has many limitations, the characteristics of the graphene, such as an ultra-large specific surface area and high conductivity, are not fully exerted, and performance indexes of key technologies, such as specific capacity and specific energy, of a chemical energy storage device cannot be significantly improved, so that the preparation and application research of the graphene energy storage device become hot spots in scientific research in recent years.
The preparation method of the graphene energy storage device is summarized and mainly comprises the following steps: a method for preparing a super capacitor by using the graphene oxide sol film, a method for preparing a graphene-based battery by using the graphene slurry mixed battery active material and the like.
The method for preparing the super-capacitor by using the graphene oxide sol film is to separate graphene oxide from a suspension to form graphite oxide or a mixture sol of the graphite oxide, reduce the graphite oxide or mix the graphite oxide with related additives to form a film, and attach the film to a current collector to prepare the super-capacitor pole piece. Although the method can be used for preparing the super capacitor electrode with higher specific capacity, the method has the disadvantages of expensive raw materials, time-consuming preparation process and incapability of realizing large-scale production.
The method for preparing the graphene-based battery by using the graphene slurry mixed battery active material comprises the steps of dispersing graphene or graphene oxide and the battery active material in a solution, uniformly mixing the graphene or graphene oxide and the battery active material by stirring or ultrasound, drying the graphene or graphene oxide compounded battery active material, and finally obtaining the graphene-modified battery electrode active material by heat treatment. The method can prepare the active material of the graphene modified battery electrode, the performance of which is improved compared with that of the original battery, but the high conductivity and the high specific surface property of the graphene are not fully exerted, so that the key performances of the specific capacity and the specific energy of the battery are not obviously improved.
The existing technology of graphene in the field of chemical energy storage application cannot meet the basic requirements of industrialization such as simple preparation method, low cost, stable and controllable product performance and the like, and particularly cannot give full play to the excellent characteristics of high conductivity, high specific surface and the like of graphene, so that the wider industrial application of graphene in the field of chemical energy storage is greatly limited.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a 3D graphene carbon-nickel hydride battery.
The purpose of the invention is realized by the following technical scheme: A3D graphene based carbon-nickel hydride battery preparation method is characterized in that graphite paper and a carbon-containing conductive adhesive are used as raw materials, one surface of the graphite paper is coated with a layer of the carbon-containing conductive adhesive, and the carbon-containing conductive adhesive is dried and cured to form an electrode material compounded by the graphite paper and the carbon-containing conductive adhesive layer; the other side of the graphite paper is divided into a polar lug area, a battery reaction area and the rest part serving as a third area, and the third area is coated with hydrophobic glue for sealing and curing; performing graphene treatment on the battery reaction zone to prepare a graphene carbon anode; the prepared graphene carbon electrode is used as a positive electrode, hydrogen storage alloy powder and hydroxyl nickel powder are mixed and pressed on a foam nickel sheet to form a battery negative electrode, a polypropylene film is used as a diaphragm, and potassium hydroxide solution is used as electrolyte, so that the 3D graphene carbon-nickel hydrogen full battery is assembled.
Preferably, the 3D graphene based carbon-nickel hydrogen full cell is a two-electrode cell or a three-electrode cell; the 3D graphene based carbon-nickel hydrogen full cell is a three-electrode cell, and the Hg/HgO electrode is used as a reference electrode.
Preferably, the method further comprises, after subjecting the battery reaction zone to the graphitization treatment, subjecting the battery reaction zone to anodic oxidation as a battery positive electrode to form a capacity to produce a graphene-based carbon positive electrode.
Further, the graphene-based carbon anode comprises partial graphene and graphene oxide or conductive oxyhydrogen compound oxidized into graphene oxide or conductive oxyhydrogen compound, and has the storage capacity of 0.1mAh/cm2The above; at 1M-10The electrode potential in the M sulfuric acid solution relative to a standard hydrogen electrode is 0V-3V.
Specifically, the anodic oxidation formation is a three-electrode anodic oxidation formation or a two-electrode anodic oxidation formation.
Preferably, the three-electrode anodic oxidation is carried out by taking the graphene-based battery reaction zone as the working positive electrode of the battery, taking a 1M-20M sulfuric acid solution as an electrolyte solution, taking a carbon electrode, a platinum electrode or a lead electrode as a counter electrode negative electrode, taking a mercurous sulfate electrode as a reference electrode, charging the mercurous sulfate electrode by applying direct current, wherein the voltage is 0.1V-30V and the current is 0.1mA/cm 2-1000mA/cm2The time is 1s-3600s, and the constant current discharge current is 0.1mA/cm2-1000mA/cm2The discharge termination voltage is 0V to-1V, and the charge-discharge cycle is 1-1000 times.
Preferably, the two-electrode anodic oxidation formation is to use a graphene-based battery reaction zone as a battery positive electrode, a 1M-20M sulfuric acid solution as an electrolyte solution, a carbon electrode or a lead electrode as a counter electrode negative electrode, an AGM diaphragm, and charge by direct current, wherein the voltage is 0.1V-30V, and the current is 0.1mA/cm2-1000mA/cm2The time is 1s-3600s, and the constant current discharge current is 0.1mA/cm2-1000mA/cm2The discharge termination voltage is 0V to-1V, and the charge-discharge cycle is 1-1000 times.
Preferably, the cell reaction zone is subjected to graphene treatment and is first subjected to micro-mechanical treatment; and then performing electrochemical expansion treatment or CV scanning treatment.
Preferably, the electrochemical expansion treatment is to use the graphite part of the electrode battery reaction part as a positive electrode, 1M-20M sulfuric acid solution as electrolyte solution, a carbon electrode, a platinum electrode, a lead electrode or the like as a counter electrode, and electrifying the direct current voltage of 0.1V-30V; the current is 0.1mA/cm2-1000mA/cm2(ii) a And (3) after 1s-3600s, the graphite on the surface is peeled off, and the graphite part remained on the conductive adhesive matrix is subjected to graphene.
Preferably, the CV scanning process is performed by using the battery reaction area as a positive electrode, using a 1M-20M sulfuric acid solution as an electrolyte solution, using a carbon electrode, a platinum electrode, a lead electrode or the like as a counter electrode, using a mercurous sulfate electrode as a reference electrode, and performing CV scanning on sulfuric acid The voltage of the mercurous electrode is 0V-2V; scan rate 0.1 x 10-9-10*10-8V/S; and scanning for 1-100 times, wherein graphite on the surface falls off, and part of graphite remained on the conductive adhesive layer is subjected to graphene.
Preferably, the graphite paper is natural expanded graphite paper or artificial graphite paper.
Preferably, the carbon-containing conductive adhesive contains carbon including graphite powder, carbon nanotubes, graphene powder and the like, and the adhesive contains organic or inorganic hydrophobic or hydrophilic adhesive and the like.
The invention also comprises a 3D graphene carbon-nickel hydrogen battery which is prepared by the preparation method, wherein the graphene carbon electrode is used as a battery anode, hydrogen storage alloy powder and hydroxyl nickel powder are mixed and pressed on a foam nickel sheet to be used as a battery cathode, a polypropylene film is used as a diaphragm, and a potassium hydroxide solution is used as an electrolyte; the reference electrode of the three-electrode 3D graphene based carbon-nickel hydrogen battery is an Hg/HgO electrode.
Preferably, the discharge voltage platform of the two-electrode 3D graphene based carbon-nickel hydride battery is 0V-2V and comprises 1-5 voltage platforms; compared with an Hg/HgO electrode, the three-electrode 3D graphene carbon-nickel hydrogen battery is charged by direct current, the constant current of 1-15mA is 1-6V, the constant voltage of 1-6V is 1-600min, the discharge termination voltage is-1V, and the discharge voltage is flat-0.6V-5V.
Compared with the prior art, the invention has the positive effects that:
(1) on the interface of the combination of the carbon-containing conductive adhesive layer and the graphite carbon material, graphene is realized in situ by graphite, or electrochemical control anodic oxidation is further carried out on the graphene carbon layer to form a carbon hydroxide material with electricity storage activity, so that the high-specific-capacity carbon anode and the high-specific-energy 3D graphite alkylene carbon-nickel hydrogen battery are prepared.
(2) The raw materials are wide in source and low in cost, various types of graphite can be used for preparation, the preparation auxiliary materials are energy-saving and environment-friendly, and the manufacturing cost is low.
(3) The preparation method is simple and convenient, the product performance is stable and controllable, and the method is suitable for industrial production.
Drawings
FIG. 1 is an SEM image of a 3D graphene-based carbon electrode of an example of the present invention;
FIG. 2 is a schematic representation of a 3D graphene-based carbon electrode according to an embodiment of the present invention;
FIG. 3 is a schematic structural view of a two-electrode full cell comprising a 3D graphene-based carbon positive electrode according to an embodiment of the present invention;
FIG. 4 is a schematic structural view of a three-electrode full cell composed of a 3D graphene-based carbon positive electrode according to an embodiment of the present invention;
FIG. 5 is a graph of a battery discharge curve according to a first embodiment of the present invention;
FIG. 6 is a graph showing the discharge of a battery according to a second embodiment of the present invention;
FIG. 7 is a graph of the discharge curve of a battery according to a third embodiment of the present invention;
FIG. 8 is a graph of the discharge curve of a battery according to a fourth embodiment of the present invention;
FIG. 9 is a graph of the discharge curve of the battery of the fifth embodiment of the present invention;
FIG. 10 is a graph of the discharge curve of a battery according to a sixth embodiment of the present invention;
fig. 11 a graph of the discharge of a battery according to an eighth embodiment of the present invention;
FIG. 12 is a graph of the discharge curve of a battery according to example nine of the present invention;
fig. 13 is a graph of the discharge curve of a battery according to a tenth embodiment of the invention.
Detailed Description
The invention relates to a preparation method of a 3D graphene based carbon-nickel hydrogen battery, which comprises the steps of coating a layer of carbon-containing conductive adhesive 1 (shown in figure 2) on one surface of graphite paper by using the graphite paper and the carbon-containing conductive adhesive as raw materials, drying and curing to form an electrode material compounded by the graphite paper and the carbon-containing conductive adhesive layer; the other side of the graphite paper is divided into a polar lug area 2, a battery reaction area 4 and the rest part as a third area 3, and the third area 3 is coated with hydrophobic glue for sealing and curing; performing graphene treatment on the battery reaction zone 4 to prepare a graphene carbon anode; the prepared graphene carbon electrode is used as a positive electrode, hydrogen storage alloy powder and hydroxyl nickel powder are mixed and pressed on a foam nickel sheet to be used as a battery negative electrode, a polypropylene film is used as a diaphragm, and potassium hydroxide solution is used as electrolyte, so that the 3D graphene carbon-nickel hydrogen full battery is assembled.
Preferably, the 3D graphene based carbon-nickel hydride full cell is a two-electrode cell or a three-electrode cell; the 3D graphene based carbon-nickel hydride full cell is a three-electrode cell, and the Hg/HgO electrode is used as a reference electrode.
Preferably, the method further comprises, after subjecting the cell reaction zone to the graphitization treatment, subjecting the cell reaction zone to anodic oxidation as a cell positive electrode to form a volume to obtain a graphene carbon positive electrode.
Further, the graphene carbon anode comprises part of graphene and is oxidized into graphene oxide or conductive oxyhydrogen compounds, and the storage capacity of the battery or the capacitor reaches 0.1mAh/cm2The above; the electrode potential in 1M-10M sulfuric acid solution is 0V-3V relative to the standard hydrogen electrode.
Specifically, the anodic oxidation formation is a three-electrode anodic oxidation formation or a two-electrode anodic oxidation formation;
preferably, the three-electrode anodic oxidation is carried out by taking the graphene-based battery reaction zone as the working positive electrode of the battery, taking a 1M-20M sulfuric acid solution as an electrolyte solution, taking a carbon electrode, a platinum electrode or a lead electrode as a counter electrode negative electrode, taking a mercurous sulfate electrode as a reference electrode, charging the mercurous sulfate electrode by applying direct current, wherein the voltage is 0.1V-30V and the current is 0.1mA/cm 2-1000mA/cm2The time is 1s-3600s, and the constant current discharge current is 0.1mA/cm2-1000mA/cm2The discharge termination voltage is 0V to-1V, and the charge-discharge cycle is 1-1000 times.
Preferably, the two-electrode anodic oxidation is carried out by taking the graphene-based battery reaction zone as the battery positive electrode, taking 1M-20M sulfuric acid solution as electrolyte solution, taking the counter electrode negative electrode as carbon electrode or lead electrode, and using AGM diaphragm to charge by direct current, wherein the voltage is 0.1V-30V, and the current is 0.1mA/cm2-1000mA/cm2The time is 1s-3600s, and the constant current discharge current is 0.1mA/cm2-1000mA/cm2The discharge termination voltage is 0V to-1V, and the charge-discharge cycle is 1-1000 times.
Preferably, the battery reaction zone is subjected to graphene treatment and is firstly subjected to micro-mechanical treatment; and then performing electrochemical expansion treatment or CV scanning treatment.
Preferably, the electrochemical expansion treatment is to use the graphite part of the electrode battery reaction part as a positive electrode, 1M-20M sulfuric acid solution as electrolyte solution, a carbon electrode, a platinum electrode, a lead electrode or the like as a counter electrode, and electrifying the direct current voltage of 0.1V-30V; the current is 0.1mA/cm2-1000mA/cm2(ii) a And (3) after 1s-3600s, the graphite on the surface is peeled off, and the graphite part remained on the conductive adhesive matrix is subjected to graphene.
Preferably, the CV scanning treatment is to use the battery reaction area as a positive electrode, 1-20M of sulfuric acid solution as an electrolyte solution, a counter electrode such as a carbon electrode, a platinum electrode or a lead electrode, a reference electrode such as a mercurous sulfate electrode, and the voltage of the CV scanning to the mercurous sulfate electrode is 0-2V; scan rate of 0.1 x 10 -9-10*10-8V/S; and scanning for 1-100 times, wherein graphite on the surface falls off, and part of graphite remained on the conductive adhesive layer is subjected to graphene.
Preferably, the graphite paper is natural expanded graphite paper or artificial graphite paper.
Preferably, the carbon-containing conductive adhesive contains carbon including graphite powder, carbon nanotubes, graphene powder and the like, and the adhesive contains organic or inorganic hydrophobic or hydrophilic adhesive and the like.
The embodiment of the invention also comprises a 3D graphene carbon-nickel hydrogen battery which is prepared by the preparation method, wherein a graphene carbon electrode is used as a battery anode, hydrogen storage alloy powder and hydroxyl nickel powder are mixed and pressed on a foam nickel sheet to be used as a battery cathode, a polypropylene film is used as a diaphragm, and a potassium hydroxide solution is used as an electrolyte; the reference electrode of the three-electrode 3D graphene based carbon-nickel hydrogen battery is an Hg/HgO electrode.
Preferably, the discharge voltage platform of the two-electrode 3D graphene carbon-nickel hydrogen battery is 0V-2V and comprises 1-5 voltage platforms; compared with an Hg/HgO electrode, the three-electrode 3D graphene carbon-nickel hydrogen battery is charged by direct current, the constant current of 1-15mA is 1-6V, the constant voltage of 1-6V is 1-600min, the discharge termination voltage is-1V, and the discharge voltage is flat-0.6V-5V.
Specific examples are as follows.
Example one
The embodiment provides a preparation method of a 3D graphene based carbon-nickel hydride battery, which comprises the following specific steps:
(1) washing and drying a 1 cm-3 cm-thick flexible expanded graphite paper strip with the thickness of 0.05mm, and fully and uniformly stirring 96.85% of acetylene black, 1.55% of sodium carboxymethylcellulose and 1.60% of styrene butadiene rubber to prepare pasty conductive adhesive slurry; and uniformly spreading the pasty slurry on one surface of a graphite paper strip to form a layer of carbon-containing conductive adhesive 1 with the spreading thickness of 0.08mm as shown in figure 2, and then drying the spread expanded graphite-carbon-containing conductive adhesive sheet in vacuum for 5 hours at normal temperature to obtain the expanded graphite-carbon-containing conductive adhesive composite sheet.
(2) 1cm of graphite surface at one end of the expanded graphite-carbon-containing conductive adhesive composite sheet is used as a battery reaction zone 4, 1cm of graphite surface at the other end of the expanded graphite-carbon-containing conductive adhesive composite sheet is attached by a hydrophobic adhesive tape at an ear zone 2 of 1cm and 0.5cm of graphite surface at the other end of the expanded graphite-carbon-containing conductive adhesive composite sheet, the rest third zone 3 is uniformly coated by styrene butadiene rubber water, the expanded graphite-carbon-containing conductive adhesive composite sheet is dried for 2 hours at normal temperature, taken out and then is additionally coated by the styrene butadiene rubber water, and then the expanded graphite-carbon-containing conductive adhesive composite sheet is dried for 2 hours at normal temperature.
(3) Removing hydrophobic adhesive tapes on a graphite battery reaction zone 4 and a tab zone 2 of the expanded graphite-carbon-containing conductive adhesive composite sheet, adhering graphite in the battery reaction zone 4 for 3 times by using an adhesive tape, taking a graphite surface of the battery reaction zone 4 as a positive electrode, taking a counter electrode as a carbon electrode and a reference electrode as a mercurous sulfate electrode in a 10M sulfuric acid solution, and carrying out CV scanning on the mercurous sulfate electrode with the voltage of 0V-1.6V; scan rate 8.8 x 10 -8V/S; scanning for 2 circles, as shown in fig. 1, is an SEM image of the cell reaction region 4, and it can be seen from the image that the cell reaction region 4 has formed graphene.
(4) As shown in fig. 3, the battery reaction zone 4 after the treatment of (3) is used as a battery anode 5, 0.12g of hydrogen storage alloy powder and 0.48g of hydroxyl nickel powder are uniformly mixed and then pressed on a foam nickel sheet under the pressure of 20MPa to be used as a battery cathode 6, a 7MKOH solution is adopted as an electrolyte 9, a polypropylene film is used as a diaphragm 7, a two-electrode carbon-nickel-hydrogen battery is assembled, as shown in fig. 5, direct current charging is carried out, constant current is carried out, 5mA to 2.2V is carried out, constant voltage is carried out for 30min, then constant current 1mA discharging is carried out,the discharge termination voltage is 0.1V, the charge and discharge cycle is 5 times, and the formation reaches the stable capacity of 0.509mAh/cm2The median voltage is 0.673V, and the discharge voltage plateaus are 1.6V and 1.0V.
Example two:
the embodiment provides a preparation method of a 3D graphene based carbon-nickel hydride battery, which comprises the following specific steps:
(1) washing and drying a 1 cm-3 cm-thick flexible expanded graphite paper strip with the thickness of 0.05mm, and fully and uniformly stirring 96.85% of acetylene black, 1.55% of sodium carboxymethylcellulose and 1.60% of styrene butadiene rubber to prepare pasty conductive adhesive slurry; and uniformly spreading the pasty slurry on one surface of a graphite paper strip to form a layer of carbon-containing conductive adhesive 1 with the spreading thickness of 0.08mm as shown in figure 2, and then drying the spread expanded graphite-conductive adhesive sheet in vacuum for 5 hours at normal temperature to obtain the expanded graphite-carbon-containing conductive adhesive composite sheet.
(2) 1cm x 1cm of the graphite surface at one end of the expanded graphite-carbon-containing conductive adhesive composite sheet is used as a battery reaction region 4, a polar lug region 2 with 1cm x 0.5cm of the graphite surface at the other end of the expanded graphite-carbon-containing conductive adhesive composite sheet is attached by a hydrophobic adhesive tape, the rest part of the expanded graphite-carbon-containing conductive adhesive composite sheet is uniformly coated by styrene butadiene rubber water, the expanded graphite-carbon-containing conductive adhesive composite sheet is dried for 2 hours at normal temperature, taken out and coated by the styrene butadiene rubber water again, and then dried for 2 hours at normal temperature.
(3) Removing the hydrophobic adhesive tapes on the graphite battery reaction zone 4 and the tab zone 2 of the expanded graphite-carbon-containing conductive adhesive composite sheet, adhering the graphite in the battery reaction zone 4 with the adhesive tapes for 3 times, taking the battery reaction zone 4 as a positive electrode, 10M sulfuric acid solution as electrolyte solution, a counter electrode as a carbon electrode, and electrifying a direct current voltage of 2.7V; the current is 0.1mA/cm2-1000mA/cm2(ii) a The time is 30min, the graphite on the surface falls off, and the redundant graphite is washed away by pure water.
(4) As shown in fig. 3, the battery reaction zone 4 after the treatment of (3) is used as a battery anode 5, 0.12g of hydrogen storage alloy powder and 0.48g of hydroxyl nickel powder are uniformly mixed and then pressed on a foam nickel sheet under the pressure of 20MPa to be used as a battery cathode 6, a 7M KOH solution is adopted as an electrolyte 9, a polypropylene film is used as a diaphragm 7, and the carbon-nickel-hydrogen battery is assembled, as shown in fig. 6, and is charged by direct current, the constant current is 5 mA-2.2V, the constant voltage is kept for 30min, then the constant current is 1mA, and the discharging is stopped Pressing 0.1V, charging and discharging for 5 times, and forming to reach stable capacity of 0.736mAh/cm2The median voltage is 0.6661V, and the discharge voltage is 0.2V-2.05V.
Example three:
the embodiment provides a preparation method of a 3D graphene based carbon-nickel hydride battery, which includes the following specific steps:
(1) washing and drying a 1 cm-3 cm flexible expanded graphite paper strip with the thickness of 0.05mm, fully and uniformly stirring 96.85% of acetylene black, 1.55% of sodium carboxymethyl cellulose and 1.60% of styrene butadiene rubber, and mixing into pasty conductive adhesive slurry; and uniformly spreading the pasty slurry on one surface of a graphite paper strip to form a layer of carbon-containing conductive adhesive 1 with the spreading thickness of 0.08mm as shown in figure 2, and then drying the spread expanded graphite-conductive adhesive sheet in vacuum at normal temperature for 5 hours to obtain the expanded graphite-carbon-containing conductive adhesive composite sheet.
(2) And (3) attaching a 1 cm-1 cm battery reaction region 4 on one end of the graphite surface of the expanded graphite-carbon-containing conductive adhesive composite sheet, a 1 cm-0.5 cm polar lug region 2 on the other end of the graphite surface of the expanded graphite-carbon-containing conductive adhesive composite sheet by using a hydrophobic adhesive tape, uniformly coating the rest part with butadiene styrene rubber water, drying at normal temperature for 2 hours, taking out, supplementing and coating with butadiene styrene rubber water, and drying at normal temperature for 2 hours.
(3) Removing adhesive tapes on a reaction zone and a tab zone of the expanded graphite-carbon-containing conductive adhesive composite flake graphite battery, sticking the graphite on the reaction zone of the battery for 3 times by using the adhesive tapes, taking the graphite surface of the reaction zone of the battery as a positive electrode, taking a 10M sulfuric acid solution as an electrolyte solution, taking a counter electrode as a carbon electrode, and electrifying a direct current voltage of 2.7V; the current is 0.1mA/cm 2-1000mA/cm2(ii) a The time is 30min, the graphite on the surface falls off, and the constant current discharge current is 0.1mA/cm2-1000mA/cm2The discharge termination voltage is 0V to-1V, the charge and discharge cycle is 1000 times, and the excess graphite is washed away by pure water.
(4) As shown in fig. 3, the battery reaction zone 4 after the treatment of (3) is used as the battery anode 5, 0.12g of hydrogen storage alloy powder and 0.48g of hydroxyl nickel powder are uniformly mixed and then pressed on a foam nickel sheet under the pressure of 20MPa to be used as the battery cathode 6, the electrolyte 9 adopts 7M KOH solution, the polypropylene film is used as the diaphragm 7, and the two-electrode carbon-nickel-hydrogen battery is assembled, as shown in fig. 7,charging with DC at constant current of 5 mA-2.2V, constant voltage for 30min, discharging at constant current of 1mA, stopping discharging at 0.1V, and circulating for 5 times to obtain stable capacity of 0.419mAh/cm2The median voltage is 0.5997V, and the discharge voltage is 0.2V-2.05V.
Example four:
this embodiment provides a method for preparing a 3D graphene based carbon-nickel hydride battery, steps (1) and (2) are the same as those in embodiment 1, and are not described herein again, and the method further includes the following steps:
(3) removing adhesive tapes on a reaction area and a tab area of the expanded graphite-carbon-containing conductive adhesive composite sheet graphite battery, adhering the graphite on the battery reaction area for 30 times by using the adhesive tapes, taking a graphite surface of an electrode reaction part as a positive electrode, taking a counter electrode as a platinum electrode and a reference electrode as a mercurous sulfate electrode in 1M sulfuric acid solution, and carrying out CV scanning on the mercurous sulfate electrode with the voltage of 1.6-2V; scan rate of 3 × 10 -8V/S; scanning for 100 circles;
(4) as shown in fig. 3, the battery reaction zone after the treatment of (3) is used as a battery anode 5, 0.12g of hydrogen storage alloy powder and 0.48g of hydroxyl nickel powder are uniformly mixed and then pressed on a foam nickel sheet under the pressure of 20MPa to be used as a battery cathode 6, a 7M KOH solution is adopted as an electrolyte 9, a polypropylene film is used as a diaphragm 7, and a two-electrode carbon-nickel-hydrogen battery is assembled, as shown in fig. 8, the direct current charging is carried out, the constant current is 5 mA-2.2V, the constant voltage is further carried out for 30min, then the constant current is carried out, the discharge termination voltage is 0.1V, the charge-discharge cycle is carried out for 5 times, and the formation reaches the stable capacity of 0.401mAh/cm2The median voltage is 0.8361V, and the discharge voltage is 0.2V-2.05V.
Example five:
the embodiment provides a preparation method of a 3D graphene based carbon-nickel hydride battery, which comprises the following specific steps:
(1) washing and drying a 1cm x 3cm flexible expanded graphite paper strip with the thickness of 0.05mm, fully and uniformly stirring commercial epoxy AB type carbon-containing conductive adhesive and paving the mixture on one surface of the graphite paper strip, as shown in figure 2, forming a layer of carbon-containing conductive adhesive 1 with the paving thickness of 0.08mm, and then drying the paved expanded graphite-carbon-containing conductive adhesive sheet in vacuum for 5 hours at normal temperature to obtain the expanded graphite-carbon-containing conductive adhesive composite sheet.
(2) A battery reaction area with the graphite surface of 1cm x 1cm at one end of the expanded graphite-carbon-containing conductive adhesive composite sheet is attached to an electrode lug area 2 with the graphite surface of 1cm x 0.5cm at the other end of the expanded graphite-carbon-containing conductive adhesive composite sheet through a hydrophobic adhesive tape, the rest third area 3 is uniformly coated with styrene butadiene rubber water, the expanded graphite-carbon-containing conductive adhesive composite sheet is dried for 2 hours at normal temperature, taken out and then additionally coated with the styrene butadiene rubber water, and then dried for 2 hours at normal temperature.
(3) Removing adhesive tapes on a graphite battery reaction zone 4 and a tab zone 2 of the expanded graphite-carbon-containing conductive adhesive composite sheet, adhering graphite in the battery reaction zone 4 with the adhesive tapes for 30 times, taking the graphite surface of an electrode reaction zone 4 as a positive electrode, using a counter electrode as a carbon electrode and a reference electrode as a mercurous sulfate electrode in a 10M sulfuric acid solution, and carrying out CV scanning on the mercurous sulfate electrode with the voltage of 1.6-2V; scan rate of 10 x 10-8V/S; scanning for 20 circles; as shown in fig. 1, which is an SEM image of the cell reaction region 4, it can be seen that the cell reaction region 4 has formed graphene.
(4) As shown in fig. 3, the battery reaction zone 4 after the treatment of (3) is used as a battery anode 5, 0.12g of hydrogen storage alloy powder and 0.48g of hydroxyl nickel powder are uniformly mixed and then pressed on a foam nickel sheet under the pressure of 20MPa to be used as a battery cathode 6, a 7MKOH solution is adopted as an electrolyte 9, a polypropylene film is used as a diaphragm 7, and a two-electrode carbon-nickel-hydrogen battery is assembled, as shown in fig. 9, direct current charging is conducted, constant current is 5 mA-2.2V, constant voltage is further kept for 30min, then constant current is conducted, discharging is carried out, the discharging termination voltage is 0.1V, charging and discharging are carried out for 5 times, and the formation reaches the stable capacity of 0.422mAh/cm 2The median voltage is 0.7683V, and the discharge voltage is 0.2V-2.05V.
Example six:
the present embodiment provides a method for preparing a 3D graphene based carbon-nickel hydride battery, wherein steps (1) and (2) are the same as those in the fifth embodiment, and are not repeated herein, except that steps (3) and (4) are specifically as follows:
(3) removing adhesive tape on reaction zone and tab zone of expanded graphite-carbon-containing conductive adhesive composite flake graphite battery, sticking graphite on the reaction zone of battery for 100 times, using graphite surface of electrode reaction part as positive electrode, 15M sulfuric acid solution as electrolyte solution, and lead as counter electrodeThe direct current voltage is 5V; the current is 0.1mA/cm2-1000mA/cm2(ii) a The time is 60min, the graphite on the surface falls off, and the redundant graphite is washed away by pure water.
(4) As shown in fig. 3, the battery reaction zone 4 after the treatment of (3) is used as a battery anode 5, 0.12g of hydrogen storage alloy powder and 0.48g of hydroxyl nickel powder are uniformly mixed and then pressed on a foam nickel sheet under the pressure of 20MPa to be used as a battery cathode 6, a 7MKOH solution is adopted as an electrolyte 9, a polypropylene film is used as a diaphragm 7, and a two-electrode carbon-nickel-hydrogen battery is assembled, as shown in fig. 10, direct current charging is conducted, constant current is 5 mA-4.5V, constant voltage is further kept for 30min, then constant current 1mA discharging is conducted, discharging termination voltage is 0.1V, charging and discharging are circulated for 5 times, and the formation reaches stable capacity of 0.675mAh/cm 2，The median voltage is 0.7224V, and the discharge voltage is 0.2V-4.05V.
Example seven:
this embodiment provides a method for preparing a 3D graphene based carbon-nickel hydride battery, in which steps (1) and (2) are the same as those in the fifth embodiment, and are not repeated herein, except that steps (3) and (4) specifically include the following steps:
(3) removing adhesive tapes on a reaction zone and a tab zone of the expanded graphite-carbon-containing conductive adhesive composite sheet graphite battery, adhering graphite on the reaction zone graphite of the battery for 3 times by using the adhesive tapes, taking a graphite surface of an electrode reaction part as a positive electrode, taking a 10M sulfuric acid solution as an electrolyte solution, taking a counter electrode as a lead electrode, and electrifying a direct current voltage of 30V; the current is 0.1mA/cm2-1000mA/cm2(ii) a The time is 30min, the graphite on the surface falls off, and the redundant graphite is washed away by pure water.
(4) As shown in fig. 3, the battery reaction zone 4 after the treatment of (3) is used as a battery anode 5, 0.12g of hydrogen storage alloy powder and 0.48g of hydroxyl nickel powder are uniformly mixed and then pressed on a foam nickel sheet under the pressure of 20MPa to be used as a battery cathode 6, a 7MKOH solution is adopted as an electrolyte 9, a polypropylene film is used as a diaphragm 7 to assemble a two-electrode carbon-nickel-hydrogen battery, direct current charging is conducted, the constant current is 5mA to 2.2V, the constant voltage is further kept for 30min, then constant current 1mA discharging is conducted, the discharging termination voltage is 0.1V, the charging and discharging cycle is performed for 5 times, and the formation reaches the stable capacity of 0.377mAh/cm 2The median voltage is 0.8401V, and the discharge voltage is 0.2V-2.05V.
Example eight:
this embodiment provides a method for preparing a 3D graphene based carbon-nickel hydride battery, in which steps (1) and (2) are the same as those in the fifth embodiment, and are not repeated herein, except that steps (3) and (4) specifically include the following steps:
(3) as shown in fig. 2, the adhesive tapes on the reaction zone 4 and the tab zone 2 of the expanded graphite-carbon-containing conductive adhesive composite sheet graphite battery are removed, the graphite in the battery reaction zone 4 is adhered with the adhesive tapes for 3 times, the graphite surface of the electrode reaction zone 4 is used as an anode, a counter electrode is a carbon electrode and a reference electrode is a mercurous sulfate electrode in a 10M sulfuric acid solution, and the voltage of the CV scanning on the mercurous sulfate electrode is 0V-1.6V; scan rate 8.8 x 10-8V/S; scan for 2 passes.
(4) As shown in figure 4, the battery reaction zone 4 treated in the step (3) is used as a battery anode 5, 0.12g of hydrogen storage alloy powder and 0.48g of hydroxyl nickel powder are uniformly mixed and then pressed on a foam nickel sheet under the pressure of 20MPa to be used as a battery cathode 6, an Hg/HgO electrode is used as a reference electrode 8, a 7MKOH solution is adopted as an electrolyte 9 to form a three-electrode carbon-nickel-hydrogen battery, direct current charging is conducted, the constant current 5mA charging reaches 1.437V, the constant voltage 1.437V is used for 30min, and the current is 0.1mA/cm 2-1000mA/cm2Constant current discharge current 1mA, discharge termination voltage-0.683V, charge-discharge cycle more than 5 times, and as shown in FIG. 11, formation reaches stable capacity of 0.596mAh/cm2The median voltage is-0.1588V, and the discharge voltage is flat-0.4V to 1.0V.
Example nine:
a preparation method of a 3D graphene based carbon-nickel hydride battery comprises the following steps:
(1) washing and drying a 1 cm-3 cm-thick flexible expanded graphite paper strip with the thickness of 0.05mm, and fully and uniformly stirring 96.85% of acetylene black, 1.55% of sodium carboxymethylcellulose and 1.60% of styrene butadiene rubber to prepare pasty conductive adhesive slurry; and uniformly spreading the pasty slurry on one surface of a graphite paper strip to form a layer of carbon-containing conductive adhesive 1 with the spreading thickness of 0.08mm as shown in figure 2, and then drying the spread expanded graphite-carbon-containing conductive adhesive sheet in vacuum for 5 hours at normal temperature to obtain the expanded graphite-carbon-containing conductive adhesive composite sheet.
(2) 1cm of graphite surface at one end of the expanded graphite-carbon-containing conductive adhesive composite sheet is used as a battery reaction zone 4, 1cm of graphite surface at the other end of the expanded graphite-carbon-containing conductive adhesive composite sheet is attached by a hydrophobic adhesive tape at an ear zone 2 of 1cm and 0.5cm of graphite surface at the other end of the expanded graphite-carbon-containing conductive adhesive composite sheet, the rest third zone 3 is uniformly coated by styrene butadiene rubber water, the expanded graphite-carbon-containing conductive adhesive composite sheet is dried for 2 hours at normal temperature, taken out and then is additionally coated by the styrene butadiene rubber water, and then the expanded graphite-carbon-containing conductive adhesive composite sheet is dried for 2 hours at normal temperature.
(3) Removing hydrophobic adhesive tapes on a graphite battery reaction zone 4 and a tab zone 2 of the expanded graphite-carbon-containing conductive adhesive composite sheet, adhering graphite of the battery reaction zone 4 with an adhesive tape for 3 times, taking the graphite surface of the battery reaction zone 4 as a positive electrode, taking a 10M sulfuric acid solution as an electrolyte solution, taking a counter electrode as a carbon electrode, and applying a direct current voltage of 2.7V; the current is 0.1mA/cm2-1000mA/cm2(ii) a The time is 30min, the graphite on the surface falls off, and the redundant graphite is washed away by pure water.
(4) Taking the battery reaction zone 4 treated in the step (3) as a battery anode, taking a 5M sulfuric acid solution as an electrolyte solution, taking a carbon electrode as a counter electrode cathode, taking a mercurous sulfate electrode as a reference electrode, assembling a three-electrode carbon anode oxidation system, charging by electrifying direct current, charging the carbon anode to 1.437V by constant current 5mA relative to the reference electrode, then keeping the constant voltage for 30min, then discharging by constant current 1mA, stopping the discharging by-0.863.0V, circulating for 500 times, taking out the carbon anode, washing and drying by distilled water, uniformly mixing 0.12g of hydrogen storage alloy powder and 0.48g of hydroxyl nickel powder, pressing the mixture on a foam nickel sheet under the pressure of 20MPa to be used as a battery cathode, taking an Hg/HgO electrode as a reference electrode, adopting an electrolyte solution of 7MKOH to form a three-electrode carbon-nickel hydride battery, charging by electrifying direct current, keeping the constant current 5mA to 1.35V, keeping the constant voltage for 30min, then discharging by constant current 1mA, the discharge termination voltage was 0.1V, and the charge and discharge cycles were 5 times, as shown in FIG. 12, until the stable capacity reached 0.622mAh/cm 2The median voltage is-0.1479V, and the discharge voltage is flat-0.6V to 1V.
Example ten:
a preparation method of a 3D graphene based carbon-nickel-metal hydride battery comprises the following steps:
(1) washing and drying a 1cm x 3cm flexible expanded graphite paper strip with the thickness of 0.05mm, fully and uniformly stirring commercial epoxy AB type carbon-containing conductive adhesive and paving the mixture on one surface of the graphite paper strip, as shown in figure 2, forming a layer of carbon-containing conductive adhesive 1 with the paving thickness of 0.08mm, and then drying the paved expanded graphite-carbon-containing conductive adhesive sheet in vacuum for 5 hours at normal temperature to obtain the expanded graphite-carbon-containing conductive adhesive composite sheet.
(2) A battery reaction area with the graphite surface of 1cm x 1cm at one end of the expanded graphite-carbon-containing conductive adhesive composite sheet is attached to an electrode lug area 2 with the graphite surface of 1cm x 0.5cm at the other end of the expanded graphite-carbon-containing conductive adhesive composite sheet through a hydrophobic adhesive tape, the rest third area 3 is uniformly coated with styrene butadiene rubber water, the expanded graphite-carbon-containing conductive adhesive composite sheet is dried for 2 hours at normal temperature, taken out and then additionally coated with the styrene butadiene rubber water, and then dried for 2 hours at normal temperature.
(3) Removing adhesive tapes on a reaction zone and a tab zone of the expanded graphite-carbon-containing conductive adhesive composite sheet graphite battery, adhering graphite in the reaction zone of the battery for 3 times by using the adhesive tapes, taking a graphite surface of an electrode reaction part as a positive electrode, taking a 10M sulfuric acid solution as an electrolyte solution, taking a counter electrode as a carbon electrode, and electrifying a direct current voltage of 2.7V; the current is 0.1mA/cm 2-1000mA/cm2(ii) a The time is 30min, the graphite on the surface falls off, and the redundant graphite is washed away by pure water.
(4) The carbon electrode treated in the step (3) is used as a battery anode, a 5M sulfuric acid solution is used as an electrolyte solution, a counter electrode cathode is used as a carbon electrode, a mercurous sulfate electrode is used as a reference electrode, a three-electrode carbon anode oxidation system is assembled, direct current charging is carried out, the carbon anode is charged to 1.437V relative to the reference electrode under the constant current of 5mA, then constant voltage is carried out for 30min, then constant current 1mA discharging is carried out, the discharging termination voltage is-0.863.0V, charging and discharging are carried out for 500 times, the carbon anode is taken out, distilled water is washed and dried, 0.12g of hydrogen storage alloy powder and 0.48g of hydroxyl nickel powder are uniformly mixed and then pressed on a foam nickel sheet under the pressure of 20MPa to be used as a battery cathode, an Hg/HgO electrode is used as a reference electrode, an electrolyte adopts 7MKOH solution to form a three-electrode carbon-nickel hydrogen battery, as shown in figure 13, direct current charging is carried out, the constant current is 5mA to 1.35V, then the constant voltage is carried out for 30min, then discharging with constant current of 1mA, stopping discharge at voltage of 0.1V, circulating for 5 times, and forming to obtain stable capacity of 0.337mAh/cm2The above, the median voltage is-0.2486V, and the discharge voltage is flat-0.6V to 1.4V.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications can be made without departing from the inventive concept, and these modifications should also be construed as being within the scope of the present invention.

Claims (7)

1. A3D graphene based carbon-nickel hydride battery preparation method is characterized in that graphite paper and a carbon-containing conductive adhesive are used as raw materials, one surface of the graphite paper is coated with a layer of the carbon-containing conductive adhesive, and the carbon-containing conductive adhesive is dried and cured to form an electrode material compounded by the graphite paper and the carbon-containing conductive adhesive layer; the other side of the graphite paper is divided into a polar lug area, a battery reaction area and the rest part serving as a third area, and the third area is coated with hydrophobic glue for sealing and curing; performing graphene treatment on the battery reaction zone to prepare a graphene carbon anode; the prepared graphene carbon electrode is used as a positive electrode, hydrogen storage alloy powder and hydroxyl nickel powder are mixed and pressed on a foam nickel sheet to form a battery negative electrode, a polypropylene film is used as a diaphragm, and potassium hydroxide solution is used as electrolyte, so that the 3D graphene carbon-nickel hydrogen battery is assembled; the step of performing graphene treatment on the battery reaction zone comprises the step of performing micro-mechanical treatment; then carrying out electrochemical expansion treatment or CV scanning treatment; the electrochemical expansion treatment is to take the graphite part of the reaction part of the electrode battery as a positive electrode, 1-20M sulfuric acid solution as electrolyte solution, a carbon electrode, a platinum electrode or a lead electrode as a counter electrode, and electrifying with direct current voltage of 0.1-30V; the current is 0.1mA/cm 2-1000mA/cm2(ii) a After the time is 1s-3600s, the graphite on the surface falls off, and the graphite part remained on the conductive adhesive matrix is graphene; the CV scanning treatment is to use a battery reaction area as a positive electrode, 1-20M sulfuric acid solution as electrolyte solution, a counter electrode as a carbon electrode, a platinum electrode or a lead electrode, a reference electrode as a mercurous sulfate electrode, and CV scanning to the mercurous sulfate electrode with the voltage of 0-2V; the scanning rate is 0.1 × 10-9-10×10-8V/S; and scanning for 1-100 times, wherein graphite on the surface falls off, and part of graphite remained on the conductive adhesive layer is subjected to graphene.
2. The method for preparing a 3D graphene-based carbon-nickel hydrogen battery according to claim 1, wherein the 3D graphene-based carbon-nickel hydrogen battery is a two-electrode battery or a three-electrode battery; the 3D graphene based carbon-nickel hydrogen full cell is a three-electrode cell, and the Hg/HgO electrode is used as a reference electrode.
3. The method of claim 1, wherein the step of performing the graphitization treatment on the battery reaction region further comprises oxidizing the battery reaction region as a positive electrode of the battery to form a volume to obtain a graphene-based carbon positive electrode.
4. The method of manufacturing a 3D graphene-based carbon-nickel hydride battery according to claim 3, wherein the graphene-based carbon positive electrode comprises a portion of graphene and is oxidized to graphene oxide or a conductive hydrocarbon; the graphene carbon anode has the storage capacity of 0.1mAh/cm of a battery or a capacitor 2The above; the electrode potential in 1M-10M sulfuric acid solution is 0V-3V relative to the standard hydrogen electrode.
5. The method of manufacturing a 3D graphene-based carbon-nickel hydride battery according to claim 3, wherein the anodic oxidation formation is a three-electrode anodic oxidation formation or a two-electrode anodic oxidation formation;
the three-electrode anodic oxidation is carried out by taking a graphene battery reaction zone as a battery working positive electrode, taking a 1M-20M sulfuric acid solution as an electrolyte solution, taking a carbon electrode, a platinum electrode or a lead electrode as a counter electrode negative electrode, taking a mercurous sulfate electrode as a reference electrode, charging by applying direct current relative to the mercurous sulfate electrode, wherein the voltage is 0.1V-30V, and the current is 0.1mA/cm2-1000mA/cm2The time is 1s-3600s, and the constant current discharge current is 0.1mA/cm2-1000mA/cm2The discharge termination voltage is 0V to-1V, and the charge-discharge cycle is 1-1000 times;
the two-electrode anodic oxidation formation is to take a graphene battery reaction zone as a battery anode, 1-20M sulfuric acid solution as electrolyte solution, a carbon electrode or a lead electrode as a counter electrode cathode, an AGM diaphragm and direct current charging, wherein the voltage is 0.1-30V, and the current is 0.1mA/cm2-1000mA/cm2Constant current discharge for 1s-3600sThe current is 0.1mA/cm2-1000mA/cm2The discharge termination voltage is 0V to-1V, and the charge-discharge cycle is 1-1000 times.
6. A3D graphene carbon-nickel hydride battery is characterized in that the battery is prepared by the preparation method of any one of claims 1 to 5, the graphene carbon electrode is used as a battery anode, hydrogen storage alloy powder and hydroxyl nickel powder are mixed and pressed on a foam nickel sheet to be used as a battery cathode, a polypropylene film is used as a diaphragm, and a potassium hydroxide solution is used as an electrolyte; the 3D graphene based carbon-nickel hydride battery comprises a two-electrode 3D graphene based carbon-nickel hydride battery or a three-electrode 3D graphene based carbon-nickel hydride battery, and the reference electrode of the three-electrode 3D graphene based carbon-nickel hydride battery is an Hg/HgO electrode.
7. The 3D graphene-based carbon-nickel hydride battery according to claim 6, wherein the two-electrode 3D graphene-based carbon-nickel hydride battery has a discharge voltage plateau of 0V to 2V, comprising 1 to 5 voltage plateaus; compared with an Hg/HgO electrode, the three-electrode 3D graphene carbon-nickel hydrogen battery is charged by direct current, the constant current of 1-15mA is 1-6V, the constant voltage of 1-6V is 1-600min, the discharge termination voltage is-1V, and the discharge voltage is flat-0.6V-5V.
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