WO2014101863A1

WO2014101863A1 - Battery electrode having auxiliary electrode structure, and high-power battery

Info

Publication number: WO2014101863A1
Application number: PCT/CN2013/090851
Authority: WO
Inventors: 刘军; 陈勇
Original assignee: Liu Jun; Chen Yong
Priority date: 2012-12-31
Filing date: 2013-12-30
Publication date: 2014-07-03
Also published as: CN102983341A

Abstract

The present invention relates to a battery electrode having an auxiliary electrode structure, and a high-power battery. An auxiliary electrode, a battery system parameter sensor and a battery control system are provided in an anode area and/or a cathode area of a flow battery or a fuel cell, and the working time interval of the battery is divided into two sections. First, the battery works to output current to the battery control system and the current is stored by the control system, the stored energy is divided into two parts by a circuit inside the battery control system, and the energy ratio of the two parts is adjusted in a braked way by controller software or manually adjusted; the battery reenters a discharging state after electric energy stored in an active material conversion circuit in the system controller is used up, and the above process is repeated continuously; the battery in working belongs to intermittent output and the whole battery system belongs to continuous output. The power density of the battery is increased, and the battery cost is reduced.

Description

Battery electrode with auxiliary electrode structure and high power battery thereof

This application claims priority to Chinese Patent Application No. 201210588983.6, entitled "A Battery Electrode with Auxiliary Electrode Structure and Its High Power Battery", filed on December 31, 2012, the entire contents of which is hereby incorporated by reference. This is incorporated herein by reference. Technical field

The invention belongs to the technical field of new energy batteries, and relates to a battery electrode with an auxiliary electrode structure and a high power battery thereof for increasing the power density of a liquid flow battery.

Background technique

The fluid battery can directly convert the chemical energy in the liquid stream into electrical energy by discharging the reducing agent and the oxidizing agent on the electrodes on both sides of the battery. Since the energy is stored in the electrolyte of the battery, it can be stored separately by energy. To achieve unlimited battery capacity, which is suitable for large-scale energy storage, peaking of the power grid is a very promising technology relative to air energy storage and storage energy storage. At present, the main flow batteries are multi-gram sodium/bromo batteries and all-vanadium flow batteries and the like. However, due to the characteristics of the electrode itself, the discharge power density is very low. For example, the output current per unit area of the electrode of the vanadium redox flow battery is only 80 mA/cm ² , and the output power is only 0.08 ~ 0.1 W/CM ² . The hydrogen fuel cell has an output power of 0.4 to 0.6 W/cm ² in the case of a platinum catalyst. These batteries have to be used because of the use of expensive perfluorinated S-resin membranes and precious metal catalysts. Further, the flow battery and the fuel battery cannot be applied on a large scale. However, in the case where the cost of other materials cannot be rapidly reduced, it is important to increase the power density per unit area of the same battery electrode to reduce the cost of the battery system. Summary of the invention

In order to overcome the above disadvantages of the prior art, the present invention provides a battery electrode having an auxiliary electrode structure and a high power battery thereof which improve battery power density and reduce battery cost.

The technical solution adopted by the present invention to solve the technical problem is that a battery electrode having an auxiliary electrode structure includes a positive electrode, a negative electrode, an electrode separator disposed between the positive electrode and the negative electrode, and an auxiliary electrode; the auxiliary electrode includes a positive electrode auxiliary Electrode and/or negative auxiliary electrode;

The positive electrode auxiliary electrode is disposed on an inner side of the positive electrode side, and the positive electrode and the positive electrode are assisted a first diaphragm is disposed between the electrodes;

The negative electrode auxiliary electrode is disposed inside the negative electrode side, and a second separator is disposed between the negative electrode and the negative electrode auxiliary electrode.

The present invention provides a high-power battery, including a battery case, a positive electrode electrolytic solution, a negative electrode electrolytic solution, and a battery electrode according to the above technical solution, which are disposed in a cavity surrounded by the battery case; The electrode separator is disposed between the positive electrode electrolytic solution and the negative electrode electrolytic solution, and further includes a battery system parameter sensor and a battery control system. The pole, the battery system parameter sensor and the battery control system, the battery working interval is divided into two sections. First, the battery working output current is supplied to the battery control system and stored by the control system. The internal circuit of the battery control system divides the stored energy into two parts. The energy ratio of the two parts is adjusted by the controller software or manually adjusted; some of them are rectified and outputted externally, and the other part is reduced by the internal battery active substance conversion circuit to obtain a low voltage current for feedback to the electrodes of the battery and Corresponding auxiliary electrode; when the battery outputs for a certain period of time, the external output current is stopped, and the stored part of the stored electric energy is supplied to the corresponding auxiliary electrode and the electrode of the battery with a certain low voltage current, so that the electrode active in the negative electrode region of the battery The substance is oxidized on the negative electrode while obtaining a higher discharge activity on the auxiliary electrode and a positive electrode material having higher discharge activity at the auxiliary electrode, thereby realizing conversion of the electrode active material during discharge of the battery; when the active substance is converted in the system controller Circuit After completion of the storage of the power consumption, the battery enters the discharging state again, so the cycle to continue; work cell belonging to the intermittent output, the entire battery system is continuously output.

Preferably, the battery has a positive electrode, a negative electrode, a positive electrode auxiliary electrode, a negative electrode auxiliary electrode, a battery separator, a battery state sensor, and a battery system controller; a first porous diaphragm is disposed between the positive electrode and the positive electrode auxiliary electrode, a second porous diaphragm is disposed between the negative electrode and the negative electrode auxiliary electrode; the battery state sensor is configured to convert an operating state of the battery; and the battery system controller is configured to control the positive electrode, the negative electrode, the positive electrode auxiliary electrode, and the negative electrode auxiliary The electrode works.

Preferably, the battery system controller includes an active material conversion circuit, an external discharge circuit, an energy storage module, and a sensor circuit;

The sensor includes a temperature sensor, an electrolyte flow rate sensor, an electrolyte concentration sensor, and electricity Deconstruction component sensor. a first porous separator that is in contact with each other, a positive electrode auxiliary electrode that is in contact with the first porous membrane, an ion exchange membrane that is in contact with the positive electrode auxiliary electrode, a negative electrode auxiliary electrode that is in contact with the ion exchange membrane, a second porous separator that is in contact with the negative electrode auxiliary electrode, and a negative electrode that is in contact with the second porous membrane;

Or the battery having the auxiliary electrode structure includes a positive electrode, a first porous separator that is in contact with the positive electrode, a positive electrode auxiliary electrode that is in contact with the first porous separator, and a positive electrode auxiliary electrode. a third porous separator, a negative electrode auxiliary electrode that is in contact with the third porous separator, a second porous separator that is in contact with the negative electrode auxiliary electrode, and a negative electrode that is in contact with the second porous separator.

Preferably, the battery having the auxiliary electrode structure may be in the form of only the positive electrode region adopting the auxiliary auxiliary structure electrode, or only the negative electrode region may be in the form of adding the auxiliary structure electrode, or the positive electrode and the negative electrode region may be in the form of adding the auxiliary structure electrode.

In the present invention, both the positive electrode auxiliary electrode and the negative electrode auxiliary electrode have an extremely large microscopic surface area and are suitable for high-power discharge.

Preferably, the electrode potential of the negative electrode auxiliary electrode is similar to the electrode potential of the fluid battery active material in the electrolyte system and the negative electrode region, and the discharge power of the electrode can be greatly improved after the electrode active material is converted. For example, in the all-vanadium redox flow battery, the anode auxiliary electrode is Pb/PbS0 ₄ , and the electrode potential is similar to the V(II)/V(III) electrode potential of the negative vanadium flow battery, but the metal lead electrode discharge power is Greatly accelerated.

Preferably, the electrode potential of the pole auxiliary electrode of the positive electrode is similar to the electrode potential of the active material of the fluid itself in the electrolyte system, for example, in the all-vanadium flow battery, the positive electrode auxiliary electrode can be adsorbed by the porous carbon electrode. A certain concentration of [3⁄4 prime element forms Br ₂ /Br_, or forms a low concentration of ci ₂ /cr. When the electrode potential pair and the ν(ιν)/ν(ν) potential are close to the electrode potential, the former discharge The power is much higher than the latter.

Preferably, the positive electrode auxiliary electrode and the positive electrode are separated by a porous separator between the negative electrode auxiliary electrode and the negative electrode.

Preferably, the battery having the auxiliary electrode structure has an ion exchange membrane or a porous membrane between the positive electrode and the negative electrode for isolating the electrolyte in the positive electrode and the negative electrode region.

The battery with the auxiliary electrode structure can cooperate in the control system and the auxiliary electrode The liquid active material flowing through the surface of the electrode is completely discharged, so that a porous membrane can be used instead of the ion exchange membrane between the positive electrode and the negative electrode of the full flow battery.

Preferably, the current supplied to the electrode/auxiliary electrode has a current voltage of 0.1 to 0.5V. Preferably, the active material conversion circuit charges the electrode/auxiliary electrode for 0.1 second to 60 minutes.

High, liquid flow rechargeable battery, liquid flow fuel cell, metal air fuel cell, direct oxime fuel cell, hydrogen fuel cell, etc.

Preferably, the power supply of the battery pack automatic control system is provided by the battery itself. The positive effects of the present invention are: using a battery pack having an auxiliary electrolytic electrode structure to greatly increase the output power of the battery by changing the real discharge electrode of the battery, thereby reducing the flow charging battery, the liquid flow fuel cell, and the metal under other conditions. The cost of an air fuel cell, a battery such as a direct fuel cell fuel cell or a hydrogen fuel cell; the application of this type of electrode structure to a fuel cell fueled by reforming hydrogen gas can reduce a small amount of CO in a conventional reformer and lead to a catalyst containing a precious metal. Electrolyte poisoning problem; this type of electrode structure is applied to a fuel cell fueled by direct sterol, which can prevent the intermediate product generated in the catalytic oxidation of sterol of the noble metal catalyst from causing poisoning of the noble metal catalytic electrode.

DETAILED DESCRIPTION OF THE INVENTION Its high power battery is further illustrated.

The invention provides a battery electrode with an auxiliary electrode structure and a high-power battery thereof, and belongs to the technical field of new energy batteries, and relates to a battery electrode for improving the power density of a liquid flow battery, and the liquid flow using the electrode structure Both the secondary battery and the fuel cell can increase the output power and reduce the cost of the secondary fluid battery and the fuel cell for energy storage; using the electrode structure can also improve the direct sterol fuel cell and hydrogen The output power of the fuel cell.

The invention adopts an auxiliary electrode and a battery control system to increase the discharge power of the flow battery and the fuel cell electrode, and increase the power density of the battery, thereby reducing the battery cost.

The present invention provides a battery electrode having an auxiliary electrode structure including a positive electrode, a negative electrode, an electrode separator disposed between the positive electrode and the negative electrode, and an auxiliary electrode;

The auxiliary electrode includes a positive electrode auxiliary electrode and/or a negative electrode auxiliary electrode;

The positive electrode auxiliary electrode is disposed on an inner side of the positive electrode side, and a first porous separator is disposed between the positive electrode and the positive electrode auxiliary electrode;

The negative electrode auxiliary electrode is disposed inside the negative electrode side, and a second porous separator is disposed between the negative electrode and the negative electrode auxiliary electrode. Schematic diagram, wherein 11 is the negative electrode, 13 is the negative electrode auxiliary electrode, 6 is the positive electrode, 7 is the positive electrode auxiliary electrode, 10 is the second porous separator, 14 is the negative electrode auxiliary electrode, and 15 is the ion exchange membrane. An electrode separator between the positive electrode and the negative electrode. The type and source of the positive electrode, the negative electrode and the electrode separator are not particularly limited, and the battery positive electrode, the negative electrode and the electrode separator which are well known to those skilled in the art may be used, such as a positive electrode in a flow battery or a fuel cell, Negative electrode and electrode separator. Specifically, in the embodiment of the present invention, when the battery is a vanadium flow battery, the graphite sheet collector may be used, and the polypropylene fiber carbon felt electrode is used as a negative electrode, and the positive electrode may be a collector obtained from a metal titanium mesh. When the battery is a zinc-air battery, a zinc electrode, such as a porous metal zinc plate, may be used as a negative electrode; the positive electrode may be a slurry obtained by mixing carbon black, activated carbon, ^11 0 ₂ and polytetrafluoroethylene resin. The positive electrode obtained by spraying onto the nickel collecting electrode preferably has a mass ratio of carbon black, activated carbon, MnO ₂ and polytetrafluoroethylene resin of 30:40:25:5.

In the present invention, the electrode separator is used to isolate the electrolyte body of the positive electrode region and the negative electrode region, and the electrode separator is preferably an ion exchange membrane or a porous separator. In the present invention, in order to distinguish the porous membrane used here The porous separator between the separator and the electrode and the auxiliary electrode, the porous membrane used as the electrode separator in the present invention is named as the third porous membrane.

In the present invention, when the electrode separator is an ion exchange membrane, the battery electrode having the auxiliary electrode structure includes, in order, a positive electrode, a first porous separator that is in contact with the positive electrode, and the first porous membrane. a positive electrode auxiliary electrode that is in contact with each other, an ion exchange membrane that is in contact with the positive electrode auxiliary electrode, a negative electrode auxiliary electrode that is in contact with the ion exchange membrane, a second porous separator that is in contact with the negative electrode auxiliary electrode, and The second porous membrane is connected to the negative electrode. That is, viewed from the positive side of the battery electrode, the structural arrangement therein is a positive electrode, a first porous separator, a positive electrode auxiliary electrode, an ion exchange membrane, a negative electrode auxiliary electrode, a second porous membrane, and a negative electrode;

When the electrode separator is a third porous membrane, the battery electrode having the auxiliary electrode structure preferably includes a positive electrode, a first porous membrane that is in contact with the positive electrode, and a first porous membrane. a positive electrode auxiliary electrode, a third porous separator that is in contact with the positive electrode auxiliary electrode, a negative electrode auxiliary electrode that is in contact with the third porous separator, and a second porous separator that is in contact with the negative electrode auxiliary electrode, a negative electrode that is in contact with the second porous membrane. That is, from the side of the positive electrode of the battery electrode, the structural arrangement therein is a positive electrode, a first porous separator, a positive electrode auxiliary electrode, a third porous separator, a negative electrode auxiliary electrode, a second porous separator, and a negative electrode. In an embodiment of the present invention, when the battery is a vanadium flow electrode, the negative electrode auxiliary electrode may be a lead electrode, such as porous metal foam, and the positive electrode auxiliary electrode may be a polypropylene fiber carbon felt; When the battery is a zinc-air battery, the positive electrode auxiliary electrode may be sprayed on a nickel collector by a mixture of carbon black, activated carbon, NiO and polytetrafluoroethylene resin, dried at 80 ° C, and then rolled. The positive electrode auxiliary electrode preferably has a mass ratio of carbon black, activated carbon, NiO, and polytetrafluoroethylene resin of 30:40:25:5.

The first porous membrane, the second porous membrane, and the third porous membrane are preferably independently selected from the group consisting of porous fibers, as in the embodiment of the invention, the first porous membrane, the second porous membrane, and the first The three porous membrane may be a polypropylene carbon fiber felt.

In an embodiment of the present invention, the battery electrode having the auxiliary electrode structure may be a battery electrode obtained by adding only the positive electrode auxiliary electrode and the first porous separator, or may be a negative electrode auxiliary electrode and a second porous separator. The battery electrode may be a battery electrode in which a positive electrode auxiliary electrode, a first porous separator, a negative electrode auxiliary electrode, and a second porous separator are simultaneously added, which is not particularly limited in the present invention.

The present invention provides a high-power battery, comprising a battery case, a positive electrode electrolytic solution, a negative electrode electrolytic solution, and a battery electrode disposed in the above-mentioned technical solution and a cavity surrounded by the battery case, the battery electrode One end is led out by a wire; an electrode separator in the battery electrode is disposed between the positive electrode electrolytic solution and the negative electrode electrolytic solution, and further includes a battery system parameter sensor and a battery control system.

The high power battery provided by the invention is in the positive electrode region and/or the negative electrode of the flow battery or fuel cell The area is provided with an auxiliary electrode, a battery state sensor and a battery control system. The battery operation interval is divided into two sections. First, the battery operation output current is supplied to the battery control system and stored by the control system. The energy stored in the internal circuit of the battery control system is stored. Divided into two parts, the energy ratio of the two parts is controlled by the battery control system software or manually adjusted; some of them are rectified and outputted externally, and the other part is reduced by the internal battery active substance conversion circuit to obtain a low voltage current. The feedback to the electrodes of the battery and the corresponding auxiliary electrodes. When the battery is output for a certain period of time, the external output current is stopped, and the stored part of the electric energy is supplied to the auxiliary electrode and the electrode corresponding to the battery with a certain low voltage current, so that the electrode active material in the negative electrode region of the battery is oxidized on the negative electrode. At the same time, an electrode active material with higher discharge activity is obtained on the auxiliary electrode; similarly, the electrode active material with low discharge activity in the positive electrode region of the battery is reduced on the positive electrode and a positive electrode material with higher discharge activity is obtained at the auxiliary electrode, thereby realizing battery discharge. When the electrode active material is converted; when the electric energy stored in the active substance conversion circuit in the battery control system is consumed, the battery re-enters the discharge state, and thus the cycle is continued; the battery is an intermittent output during operation, and the entire battery system belongs to Continuous output. In this way, the battery output is more powerful. 2 is a cross-sectional view of the battery having the auxiliary electrode structure shown in FIG. 1. In FIG. 1, 1 is a pump, 2 is an inlet, 3 is an outlet, 4 is a negative electrode region, and 5 is a positive electrode region; In the middle, 6 is the positive electrode, 7 is the positive electrode auxiliary electrode, 8 is the positive electrode electrolytic solution, 9 is the positive electrode auxiliary electrode, 10 is the separator, 11 is the negative electrode, 12 is the negative electrode electrolytic solution, 13 is the negative electrode auxiliary electrode, 14 is the negative electrode auxiliary electrode, 15 is an ion exchange membrane.

The high-power battery provided by the present invention includes a battery case. The shape, size and material of the battery case are not particularly limited in the present invention, and a battery case known to those skilled in the art may be used, such as the battery case. The material may be an ABS plastic plate, and the battery case may have a rectangular parallelepiped shape.

In the present invention, the battery has a positive electrode, a negative electrode, a positive electrode auxiliary electrode, a negative electrode auxiliary electrode, a battery separator, a positive electrode electrolytic solution, a negative electrode electrolytic solution, a battery state sensor, and a battery system controller; and the battery system controller includes An active material conversion circuit, an external discharge circuit, an energy storage module, and a sensor circuit; in the present invention, the battery system controller receives a current outputted by the battery, and the received current is stored by the energy storage module, and is stored The energy is divided into two parts, the energy ratio of the two parts is adjusted by the battery control system software or manually adjusted; A portion of the energy is rectified and outputted to the outside through the external discharge circuit, and another portion is reduced in voltage by the active material conversion circuit to obtain a low voltage current, and the low voltage current is supplied to the electrode and the corresponding auxiliary electrode, and the active material is converted. The circuit charges the electrode/auxiliary electrode. In the present invention, the positive electrode is connected to a positive terminal of the battery system controller, the negative electrode is connected to a negative terminal of the battery system controller, and the positive auxiliary electrode and the battery system are controlled. A positive auxiliary electrode terminal is connected to the negative electrode auxiliary electrode and a negative auxiliary electrode terminal in the battery system controller.

In the present invention, the current supplied to the electrode/auxiliary electrode is preferably 0.1 V to 0.5 V, more preferably 0.2 V to 0.4 V; and the time during which the active material conversion circuit charges the electrode/auxiliary electrode is preferably It is from 0.1 second to 60 minutes, more preferably from 1 second to 55 minutes, and most preferably from 10 seconds to 50 minutes.

In the present invention, the battery state sensor includes a temperature sensor, an electrolyte flow rate sensor, an electrolyte concentration sensor, and an electrolyte composition sensor for sensing and adjusting an operating temperature of the battery, a flow rate of the electrolyte, a concentration of the electrolyte, and a composition of the electrolyte, Thereby adjusting the working state of the battery.

In the present invention, the electrode system in the battery having the auxiliary electrode structure is the battery electrode having the auxiliary electrode structure described in the above technical solution, and the battery having the auxiliary electrode structure may be only the positive electrode region adopting the auxiliary structure. In the form of an electrode, only the negative electrode region may be in the form of an auxiliary structure electrode, or the positive electrode and the negative electrode region may be in the form of an auxiliary structure electrode, and no particular limitation is imposed on the invention. The type of the positive electrode electrolyte body and the negative electrode electrolyte body of the present invention is not particularly limited, and an electrolyte solution well known to those skilled in the art may be used. In an embodiment of the present invention, when the battery is a zinc-air battery, the positive electrode electrolyte body and the negative electrode electrolyte body may be a potassium hydroxide solution having a mass concentration of 30%; when the battery is a vanadium flow battery The positive electrode electrolyte body includes V0 ₂ ⁺ , 2 mol/L of sulphuric acid and 0.5 mol/L in a molar concentration of 2 mol/L.负极, the negative electrode electrolyte body includes V ²⁺ , 2 mol/L sulfuric acid, and 0.5 mol/L Cl_ at a molar concentration of 2 mol/L.

In an embodiment of the present invention, the battery case may be provided with an opening, which is an inlet of an electrolyte and an outlet of an electrolyte. Specifically, a positive electrode region of the battery case is provided with an electrolyte inlet of a positive electrode region. And a positive electrode region electrolyte outlet; the negative electrode region of the battery case is provided with a negative electrode region electrolyte inlet and a negative electrode region electrolyte outlet. In an embodiment of the invention, the positive electrode region electrolyte is advanced An electrolyte outlet of the port and the positive electrode region is disposed on a sidewall on the same side of the battery case, the electrolyte inlet of the positive electrode region is disposed below the electrolyte outlet of the positive electrode region; and the electrolyte inlet and the negative electrode region of the negative electrode region are electrolyzed The liquid outlet is disposed on a side wall of the same side of the battery case, and the negative electrode area electrolyte inlet is disposed below the electrolyte outlet of the negative electrode area.

In order to facilitate the transportation of the electrolyte, in the embodiment of the present invention, a pump is installed at the inlet of the electrolyte. Specifically, a first pump is installed at the inlet of the electrolyte in the positive electrode region, and an electrolyte is disposed in the negative electrode region. A second pump is installed at the inlet.

In the high-power battery provided by the present invention, in the electrolyte system, the electrode potential of the negative electrode auxiliary electrode is similar to the electrode potential of the fluid battery active material in the negative electrode region, and the discharge of the electrode can be improved after the electrode active material is converted. power. In an embodiment of the invention, for example, in the all-vanadium redox flow battery, the negative auxiliary electrode pair is Pb/PbS0 ₄ , the electrode potential of the electrode pair Pb/PbS0 ₄ and the total vanadium flow battery negative electrode region electrode pair V The electrode potentials of (II)/V(III) are similar, and the discharge power of the metal lead electrode is greatly accelerated.

In the high-power battery provided by the present invention, in the electrolyte system, the electrode potential of the positive electrode auxiliary electrode is close to the electrode potential of the active material of the fluid itself, and the discharge power of the electrode can be provided after the electrode active material is converted. In an embodiment of the present invention, for example, in the all-vanadium redox flow battery, the positive electrode auxiliary electrode may adsorb a certain concentration of halogen element to form a Br ₂ /Br- or a low concentration of C1 ₂ /C1_ for the porous carbon electrode. The electrode potential pair and the V(IV)/V(V) potential are similar to the electrode potential, and the former has a much higher discharge power than the latter.

In the high-power battery provided by the present invention, between the positive electrode auxiliary electrode and the positive electrode, a porous separator is isolated between the negative electrode auxiliary electrode and the negative electrode.

The battery having the auxiliary electrode structure has an ion exchange membrane or a porous separator between the positive electrode and the negative electrode for isolating the electrolyte in the positive electrode and the negative electrode region.

The battery with the auxiliary electrode structure can completely discharge the liquid active material flowing through the electrode surface under the joint action of the control system and the auxiliary electrode, so a porous diaphragm can be used instead of the positive electrode and the negative electrode of the full flow battery. Ion exchange membrane. The output power of batteries, liquid fuel cells, metal air fuel cells, direct methanol fuel cells, hydrogen fuel cells, etc.

The battery control system in the high power battery having the auxiliary electrode structure provided by the present invention is preferably an automatic control system, and the power supply of the automatic control system is preferably provided by the battery itself.

The invention uses the battery pack with the auxiliary electrolysis electrode structure to greatly increase the output power of the battery by changing the real discharge electrode of the battery, thereby reducing the flow charging battery, the liquid flow fuel cell, the metal air fuel cell directly under other conditions. The cost of a battery such as a sterol fuel cell or a hydrogen fuel cell; applying this type of electrode structure to a fuel cell fueled by reforming hydrogen can reduce the problem of electrode poisoning of a noble metal-containing catalyst caused by a small amount of CO in a conventional reformer; This type of electrode structure is applied to a fuel cell fueled by direct sterol, which can prevent the noble metal catalyst from poisoning problems caused by intermediate products generated in the catalytic oxidation of sterol.

In order to further explain the present invention, the battery electrode having the auxiliary electrode structure and the high power battery thereof provided by the present invention are described in detail below with reference to the embodiments, but they are not to be construed as limiting the scope of the present invention.

The following embodiment employs the structure shown in Figs. 1 to 3 to prepare a battery having an auxiliary electrode structure.

Example 1:

According to the structure shown in Figure 1, a plastic groove of 20 mm long x 100 mm x 20 is made of ABS plastic plate and a proton exchange membrane is installed in the middle of the groove as a separator for the fluid battery, and the plastic tank is divided into 10 X 100 X 150 mm. The two parts are respectively a negative electrode region and a positive electrode region, and the side walls of the two portions are respectively opened to form an inlet and outlet of the fluid battery electrolyte, and the corresponding micro pump is connected as a circulating pump of the electrolyte;

According to Fig. 2, a graphite sheet having a length X width of 100 X 150 mm and a thickness of 1 mm was used as a collecting electrode, and was cut into a 150 150 electrode by heat treatment at 400 ° C for 24 hours. A porous fiber cloth having a length X and a width of 105 X 155 mm was cut as a separator. A porous metal foam lead having a length x width of 100 X 150 mm and a thickness of 1 mm was used as the negative electrode auxiliary electrode. The graphite collector, the polypropylene carbon fiber felt electrode, the separator, and the auxiliary lead electrode are pressed in order and placed in the negative electrode region of the processed plastic tank.

A metal titanium mesh having a length X width of 100 X 150 mm and a thickness of 1 mm is used as a collector to The polypropylene carbon fiber felt was heat-treated at 400 ° C for 24 hours, and then heat-treated and then cut into 100 150, which were a positive electrode and a positive electrode auxiliary electrode, respectively. A porous fiber cloth having a length X width of 105 X 155 mm was cut as a separator. The titanium mesh collector, the polyacrylonitrile carbon fiber felt positive auxiliary electrode, the separator, and the polypropylene carbon fiber felt positive electrode are pressed in order and placed in the positive electrode region of the processed plastic tank.

The electrolyte component in the negative electrode region is 2 mol/L of V ²⁺ , 2 mol/L of sulphuric acid, and 0.5 mol/L of CT; the electrolyte in the positive electrode region is 2 mol/L of V0 ₂ ⁺ , 2 mol/L of sulfuric acid, 0.5 mol/L of Cr.

The auxiliary electrodes in the battery are respectively connected to the terminals of the corresponding auxiliary electrodes of the control system, and the electrodes are respectively connected with the corresponding terminals of the control system, and connected to the electrolyte circulation system to obtain the auxiliary electrode structure. An all-vanadium flow fluid battery.

When the battery is working, the voltage output from the control system to the positive/positive auxiliary electrode is 0.2 volts. At this time, the reaction in the positive electrode region is vo ₂ ⁺ +cr- - vo ²⁺ + ci ₂ (adsorbed by the polypropylene-based carbon felt electrode). The ci ₂ in the adsorbed state at the time of discharge is discharged through the positive electrode of the polypropylene fiber carbon fiber felt. The output voltage of the control system to the negative/negative auxiliary electrode is 0.1 volt, and the reaction occurs at this time as PbS0 ₄ + 2V ²⁺ - Pb + S0 ₄ ² " + 2V ³⁺ , which is discharged by the metal lead electrode during discharge. The charging and discharging time of the control system to the battery pack is intelligently controlled by the magnitude of the load power, so that the battery operates at the maximum efficiency. The operation of the auxiliary electrode makes the average output power of the entire vanadium flow battery more than the vanadium without the auxiliary electrode. The output power of the flow battery is increased by 5 times. The electrode structure of the battery is changed from a common all-vanadium flow battery structure to a metal lead/chlorine battery structure.

Example 2:

According to the scheme described in the drawing, a plastic groove of length X width X height 100 X 50 X 70 mm is made of ABS plastic plate and a hole of 80 60 is opened in one side wall of the groove. According to Figure 3, the foamed nickel with a length X width of 90 60 mm and a thickness of 1 mm is used as a collector, and then carbon black, activated carbon, NiO, and polytetrafluoroethylene resin are arranged in a ratio of 35:35:15:15. The material was uniformly sprayed onto the foamed nickel collector by spraying, and dried at 80 ° C and then rolled to obtain a positive electrode auxiliary electrode. The same processing size length X width is 90 X 60mm, the thickness of lmm foam nickel is the collector, and then (3 crystal carbon black, activated carbon and Mn0 ₂ , polytetrafluoroethylene resin according to 30:30: 15: 25 The ratio is configured such that the slurry is uniformly sprayed onto the foamed nickel collector by spraying, and is sufficiently dried after being dried at 80 ° C to obtain a positive electrode. The porous fiber cloth having a length X width of 90 X 60 mm is cut. As a separator, the positive electrode auxiliary electrode, the separator, and the positive electrode are pressed in order and fixed at the opening of the plastic tank and will be positive. The gap between the pole and the plastic groove is sealed so that the positive electrode auxiliary electrode faces the inside of the plastic groove. 30% KOH as electrolyte in the electrolytic cell,

The porous metal zinc plate is a negative electrode. The auxiliary electrodes in the battery are respectively connected to the corresponding auxiliary electrode terminals of the control system, and the positive and negative electrodes are respectively connected to the electrode terminals corresponding to the control system to obtain the zinc air fuel cell having the auxiliary electrode structure.

When the battery is working, the voltage output from the control system to the positive/positive auxiliary electrode is 0.2 volts. At this time, the reaction in the positive electrode region is NiO + MnO(OH) - NiO(OH) + ΜηΟ, 0 ₂ (from air) + MnO MnO(OH) is discharged through the positive electrode auxiliary electrode during discharge. The zinc-air battery has an output voltage of 1.7V, which is about 0.3V higher than the direct output voltage of a normal zinc-air battery. The charging and discharging time of the control system to the battery pack is intelligently controlled by the magnitude of the load power. Through the operation of the auxiliary electrode, the average output power of the entire zinc-air battery is increased by 4 times compared with the output of the zinc-air battery without the auxiliary electrode. The battery electrode structure is converted from a common metal zinc electrode/air electrode structure to a metal zinc electrode/hydroxyl group. Nickel oxide electrode structure.

The above description of the embodiments is merely to assist in understanding the method of the present invention and its core idea. It is to be understood that those skilled in the art can make various modifications and changes to the present invention without departing from the spirit and scope of the invention. Various modifications to these embodiments are obvious to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the present invention is not to be limited to the embodiments shown herein, but is to be accorded to the broadest scope of the principles and novel features disclosed herein.

Claims

Rights request

1. A battery electrode having an auxiliary electrode structure and a high-power battery thereof, characterized in that: in the liquid number sensor and the battery control system, the interval of the battery is divided into two sections, first letting the battery work output current to the battery control system and Stored by the control system, the internal circuit of the battery control system divides the stored energy into two parts. The energy ratio of the two parts is adjusted by the controller software or manually adjusted; some of them are rectified and output externally, and the other part is internally charged. The active material conversion circuit reduces the voltage to obtain a low-voltage current for supplying the electrode of the battery and the corresponding auxiliary electrode; when the battery outputs for a certain period of time, stopping the external output current, the system controller uses the stored partial power to a certain low-voltage current. Providing to the auxiliary electrode and the electrode corresponding to the battery, so that the electrode active material in the negative electrode region of the battery is oxidized on the negative electrode and the electrode active material having higher discharge activity is obtained on the auxiliary electrode; and the positive electrode material having higher discharge activity is obtained, thereby Realize electrode live when discharging battery Conversion of the substance; when the stored energy stored in the active substance conversion circuit in the system controller is consumed, the battery re-enters the discharge state, and thus continues to cycle; the battery in operation is an intermittent output, and the entire battery system is a continuous output. .

2. The battery electrode having an auxiliary electrode structure according to claim 1, and the high power battery thereof, wherein: the battery has a positive electrode, a negative electrode, a positive electrode auxiliary electrode, a negative electrode auxiliary electrode, a battery separator, a battery state sensor, and a battery. The system controller; the structure from the positive electrode to the negative electrode is sequentially a positive electrode, a porous separator, a positive electrode auxiliary electrode, an ion exchange membrane, a negative electrode auxiliary electrode, a porous separator, a negative electrode or a positive electrode, a porous separator, a positive electrode auxiliary electrode, a porous separator, and a negative electrode. Auxiliary electrode, porous separator and negative electrode.

3. The battery electrode having the auxiliary electrode structure and the high power battery thereof according to claim 2, wherein: the battery system controller has an active material conversion circuit, an external discharge circuit, an energy storage module, and a sensor circuit; The sensor has a sensor of the type such as a temperature sensor, an electrolyte flow rate sensor, an electrolyte concentration, and an electrolyte composition sensor.

4. The battery electrode having the auxiliary electrode structure and the high power battery thereof according to claim 2, wherein: the positive electrode auxiliary electrode and the negative electrode auxiliary electrode both have an ultra-large micro surface area, which is suitable for High-power discharge; the electrode potential of the negative electrode auxiliary electrode should be similar to the electrode potential of the fluid battery active material in the electrolyte system and the negative electrode region, and the discharge power of the electrode can be greatly improved after the electrode active material is converted; In the flow battery, the negative electrode auxiliary electrode is Pb/PbS0 ₄ , and the electrode potential is similar to the ν(π)/ν(πι) electrode potential of the negative electrode region of the all-vanadium flow battery, but the discharge power of the metal lead electrode is greatly accelerated; The electrode potential of the positive electrode auxiliary electrode is similar to the electrode potential of the active material of the fluid itself in the electrolyte system; in the all-vanadium flow battery, the positive electrode auxiliary electrode can adsorb a certain concentration of halogen element to form a Br ₂ for the porous carbon electrode. /Br_, or form a low concentration of C1 ₂ /C1_, in the case where the electrode potential pair and the V(IV)/V(V) potential are close to the electrode potential, the former has a large discharge power.

13⁄4 in the latter.

The battery electrode having the auxiliary electrode structure and the high-power battery thereof according to claim 2 or 4, wherein: the positive electrode auxiliary electrode and the positive electrode, and the negative electrode auxiliary electrode and the negative electrode are separated by a porous diaphragm; An ion exchange membrane or a porous membrane is present between the positive electrode and the negative electrode to isolate the electrolyte in the positive and negative electrode regions.

6. The battery electrode having an auxiliary electrode structure and the high power battery thereof according to claim 1, wherein said battery having an auxiliary electrode structure is caused to flow through the electrode under the joint action of said control system and said auxiliary electrode The liquid active material on the surface is completely discharged. In the full-flow battery, a porous membrane is used instead of the ion exchange membrane between the positive electrode and the negative electrode.

7. The battery electrode having an auxiliary electrode structure according to claim 1, and a high-power battery thereof, wherein: the current supplied to the electrode/auxiliary electrode is 0.1 to 0.5V.

The battery electrode having the auxiliary electrode structure according to claim 1 or 3, and the high-power battery thereof, wherein: the active material conversion circuit charges the electrode/auxiliary electrode in a period of 0.1 second to 60 minutes. .

9. The battery electrode with an auxiliary electrode structure according to claim 1, and a high-power battery thereof, characterized in that: a high-power battery having an auxiliary electrode structure is used for a liquid flow rechargeable battery, a liquid flow fuel cell, a metal air fuel cell, In a direct methanol fuel cell or a hydrogen fuel cell, the output power of the liquid flow rechargeable battery, the liquid flow fuel cell, the metal air fuel cell, the direct methanol fuel cell or the hydrogen fuel cell is increased.

10. The battery electrode having an auxiliary electrode structure according to claim 1, and a high power battery thereof, wherein: a power source of the battery control system in the battery having the auxiliary electrode structure is used by the battery itself Ten

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TS8060/ClOZN3/X3d £98 Li OZ OAV