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 hydrogen battery.
The purpose of the invention is realized by the following technical scheme: a preparation method of a 3D graphene based carbon-nickel hydrogen battery 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 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 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 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 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; 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/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 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 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 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.
Compared with the prior art, the invention has the following positive effects:
(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.
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 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; 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 using a graphene-based cell reaction zone as an electrolyteThe cell working anode is 1-20M sulfuric acid solution as electrolyte solution, the counter electrode cathode is carbon electrode, platinum electrode or lead electrode, the reference electrode is mercurous sulfate electrode, and direct current charging is conducted on the reference electrode relative to the mercurous sulfate electrode, the voltage is 0.1-30V, 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 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.
(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, and a two-electrode carbon-nickel-hydrogen battery is assembled, as shown in fig. 5, the direct current charging is carried out, the constant current is 5 mA-2.2V, the constant voltage is further kept for 30min, then the constant current is 1mA discharging, the discharging termination voltage is 0.1V, the charging and discharging cycle is carried out for 5 times, and the formation reaches the stable capacity of 0.509mA2The 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 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 with a hydrophobic adhesive tape at a polar lug zone 2 of 1cm and 0.5cm, the rest part of the expanded graphite-carbon-containing conductive adhesive composite sheet is uniformly coated with styrene butadiene rubber water, the expanded graphite-carbon-containing conductive adhesive composite sheet is dried at normal temperature for 2 hours, taken out and coated with the styrene butadiene rubber water.
(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 the graphite of the battery reaction zone 4 with an adhesive tape 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, the direct current charging is carried out, the constant current is 5mA to 2.2V, the constant voltage is further carried out for 30min, then the constant current is carried out, the discharging termination voltage is 0.1V, the charging and discharging cycle is carried out for 5 times, and the formation reaches the stable capacity of2The 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 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) The expanded graphite-carbon-containing conductive adhesive composite sheet is characterized in that a battery reaction area 4 with one graphite surface being 1cm x 1cm is arranged at one end of the expanded graphite-carbon-containing conductive adhesive composite sheet, a polar lug area 2 with the graphite surface being 1cm x 0.5cm 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.
(3) Removing adhesive tapes on a reaction zone and a tab zone of the expanded graphite-carbon-containing conductive adhesive composite sheet graphite battery, sticking the graphite in 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/cm2-1000mA/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 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. 7, 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 0.419mA2The 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 reaction region of the battery after the treatment (3) was used as the positive electrode 5 of the battery, and 0.12g of the reaction region was storedAfter being uniformly mixed, the hydrogen alloy powder and 0.48g of hydroxyl nickel powder are pressed on a foam nickel sheet under the pressure of 20MPa to be used as a battery cathode 6, 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 figure 8, the two-electrode carbon-nickel hydrogen battery is charged by direct current, the constant current is 5mA to 2.2V, the constant voltage is 30min, then the constant current is 1mA discharges, 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 0.401mAh2The 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 region 4 treated in (3) was used as a battery positive electrode 5, and 0.12g of a hydrogen-absorbing alloy was addedAfter the powder and 0.48g hydroxyl nickel powder are uniformly mixed, the mixture is pressed on a foam nickel sheet under the pressure of 20MPa to be used as a battery cathode 6, 7MKOH solution is adopted as electrolyte 9, a polypropylene film is used as a diaphragm 7, a two-electrode carbon-nickel hydrogen battery is assembled, as shown in figure 9, direct current charging is conducted, constant current is 5mA to 2.2V, constant voltage is further kept for 30min, then constant current 1mA discharging is conducted, discharging termination voltage is 0.1V, charging and discharging circulation is conducted for 5 times, and the formation reaches the stable capacity of 0.422mAh/cm2The median voltage is 0.7683V, and the discharge voltage is 0.2V-2.05V.
Example six:
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 the graphite in the reaction zone of the battery for 100 times by using the adhesive tapes, taking a graphite surface of an electrode reaction part as a positive electrode, taking a 15M sulfuric acid solution as an electrolyte solution, taking a counter electrode as a lead electrode, and electrifying a direct current voltage of 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/cm2,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/cm2The 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 fig. 4, 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 nickel hydroxyl powder are uniformly mixed and then pressed on a nickel foam sheet under the pressure of 20MPa to be used as the battery cathode 6, an Hg/HgO electrode is used as the reference electrode 8, the electrolyte 9 adopts 7MKOH solution to form a three-electrode carbon-nickel-hydrogen battery, and direct current charging is carried outThe constant current 5mA charging is up to 1.437V, the constant voltage 1.437V is up to 30min, and the current is 0.1mA/cm2-1000mA/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-metal 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.
(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) The battery reaction zone 4 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 a carbon electrode, a mercurous sulfate electrode is used as a reference electrode, a three-electrode carbon anodic oxidation system is assembled, and direct current is introducedCharging by electricity, charging the carbon anode to 1.437V by constant current 5mA relative to a reference electrode, then performing constant voltage 30min, then discharging by constant current 1mA, ending the discharge at voltage of-0.863.0V, performing charge-discharge circulation for 500 times, taking out the carbon anode, washing with distilled water, drying, 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 serve as a battery cathode, taking an Hg/HgO electrode as a reference electrode, adopting 7MKOH solution as electrolyte to form a three-electrode carbon-nickel hydrogen battery, charging by direct current, performing constant current 5mA to 1.35V, performing constant voltage 30min, then discharging by constant current 1mA, ending the discharge at voltage of 0.1V, performing charge-discharge circulation for 5 times, and as shown in figure 12, and converting to a stable capacity of 0.622mAh/cm2The 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/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) 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, 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.