CN110556554A - Electrode protection method for metal fuel cell - Google Patents

Electrode protection method for metal fuel cell Download PDF

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Publication number
CN110556554A
CN110556554A CN201910867847.2A CN201910867847A CN110556554A CN 110556554 A CN110556554 A CN 110556554A CN 201910867847 A CN201910867847 A CN 201910867847A CN 110556554 A CN110556554 A CN 110556554A
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Prior art keywords
fuel cell
metal fuel
voltage
reverse
electrode
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CN201910867847.2A
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CN110556554B (en
Inventor
侯武岱
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Shenzhen Shengtong New Energy Technology Co Ltd
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Shenzhen Shengtong New Energy Technology Co Ltd
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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
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04694—Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
    • H01M8/04858—Electric variables
    • H01M8/04865—Voltage
    • H01M8/04873—Voltage of the individual fuel cell
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04694—Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
    • H01M8/04955—Shut-off or shut-down of fuel cells
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention provides an electrode protection method of a metal fuel cell. The electrode protection method of the metal fuel cell comprises the following steps: applying a reverse voltage to the metal fuel cell, wherein the direction of the reverse voltage is opposite to the discharge direction of the metal fuel cell. The invention has the beneficial effects that: in the electrode protection method of the metal fuel cell provided by the invention, the reverse voltage is applied to the metal fuel cell, so that the problem of reduction of cell efficiency caused by colloid in the discharging process can be solved, the anode electrode can be protected, and the increase of electrode polarization resistance caused by self-corrosion of the anode electrode can be avoided.

Description

Electrode protection method for metal fuel cell
Technical Field
The invention relates to the technical field of metal-air batteries, in particular to an electrode protection method of a metal fuel battery.
Background
The metal fuel cell is an electrochemical reaction device which adopts metal (such as magnesium, aluminum, zinc and the like) as anode fuel, oxygen in the air as oxidant and alkali liquor or neutral salt water as electrolyte solution, and has the characteristics of high energy density, long dry-state storage life, no pollution of reactants and products, quiet work and the like. Therefore, the metal fuel cell has wide application prospect in various fields of portable power supplies such as communication power supplies, field emergency power supplies, illumination power supplies, reserve power supplies and the like. The metal resources such as magnesium, aluminum, zinc and the like in China are rich and low in price, and the development of the metal fuel cell technology has important significance for adjusting the industrial structure of the metals such as magnesium, aluminum, zinc and the like and perfecting the technical reserve of the portable chemical power supply.
The existing metal fuel cell can generate a large amount of hydrogen compounds in the process of electrolyte reaction, and the hydrogen compounds are all presented in a colloid form. The colloids have the property of electrophoresis, so that the colloids are attached to the electrode under the action of an electric field during reaction, internal resistance of the electrode is increased during discharge, and efficiency of the battery is reduced; moreover, the colloid adhering to the electrode also blocks the air permeability of the air electrode, reducing the life of the catalyst layer.
In addition, when the metal fuel cell is left standing for a long time and is not discharged, the anode immersed in the electrolyte slowly undergoes an oxidation reaction with oxygen dissolved in the electrolyte, resulting in oxidation of the surface of the anode electrode resulting in self-corrosion.
Disclosure of Invention
The invention aims to solve the defects in the prior art and provides an electrode protection method of a metal fuel cell.
A method of protecting an electrode of a metal fuel cell, comprising the steps of: applying a reverse voltage to the metal fuel cell, wherein the direction of the reverse voltage is opposite to the discharge direction of the metal fuel cell.
Preferably, when the metal fuel cell is in a state of discharging to a load, a reverse pulse voltage V is applied to the metal fuel cellPulseSaid reverse pulse voltage VpulseIs greater than the discharge voltage V of the metal fuel cellPutThe voltage value of (2).
Preferably, the reverse pulse voltage VPulseThe effective voltage of the middle duty ratio is 0.9V-3V.
Preferably, when the metal fuel cell is in an off-load state, a reverse rated voltage V is applied to the metal fuel cellForehead (forehead)said reverse rated voltage VForehead (forehead)Is greater than the discharge voltage V of the metal fuel cellPutThe voltage value of (2).
Preferably, after the metal fuel cell is applied with the reverse rated voltage for a period of time, the metal fuel cell is started to perform one or more times of discharge.
Preferably, the reverse rated voltage VForehead (forehead)the static voltage of (A) is 0.9V-3V.
Preferably, before the step of applying a reverse voltage to the metal fuel cell, the reverse voltage being opposite to a discharge voltage of the metal fuel cell, the method further comprises the steps of: and detecting the internal resistance of the metal fuel cell, judging whether the internal resistance is greater than a trigger value, and if so, executing the step of applying reverse voltage to the metal fuel cell.
The invention has the beneficial effects that:
In the electrode protection method of the metal fuel cell provided by the invention, the reverse voltage is applied to the metal fuel cell, so that the problem of reduction of cell efficiency caused by colloid in the discharging process can be solved, the anode electrode can be protected, and the increase of electrode polarization resistance caused by self-corrosion of the anode electrode can be avoided.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides an electrode protection method of a metal fuel cell, which comprises the following steps:
The method comprises the following steps: detecting the internal resistance of the metal fuel cell, judging whether the internal resistance is greater than a trigger value, and if so, executing a second step;
Step two: applying a reverse voltage to the metal fuel cell, wherein the direction of the reverse voltage is opposite to the discharge direction of the metal fuel cell.
Specifically, in the first step, the internal resistance of the metal fuel cell is calculated by detecting the current and the voltage of the metal fuel cell; establishing an internal resistance change table of the metal fuel cell in the whole natural discharge process through a control chip and setting a trigger value; and triggering an electrode protection mechanism when the detected internal resistance exceeds a trigger value, and executing the second step.
Alternatively, step one may be omitted. In some simple systems, the electrode protection mechanism may also be triggered periodically. Namely, after the metal fuel cell is naturally discharged for a set time, the second step is automatically performed to protect the electrode.
In the second step, the reverse voltage is an applied voltage with a voltage direction opposite to the discharge direction of the battery. Namely, the metal fuel cell is applied with reverse voltage through an external power supply, the metal fuel cell is prevented from discharging, and reverse current opposite to the direction of the discharging current is formed in the metal fuel cell, so that the internal electric field of the cell is changed.
The pulsed voltage is applied in different ways for metal fuel cells in different states:
1. When the metal fuel cell is in a state of discharging to a load, applying a reverse pulse voltage V to the metal fuel cellPulseSaid reverse pulse voltage VpulseIs greater than the discharge voltage V of the metal fuel cellPutThe voltage value of (2). Preferably, the reverse pulse voltage VPulseThe effective voltage of the medium duty ratio is 0.9V-3V, and the duty ratio is 10-70%.
For example, a reverse pulse voltage with a voltage of 3.0V, a duty cycle of 70%, and a frequency >50HZ is applied to the metal fuel cell in reverse. It will be appreciated that during the remaining 30% of the cycle outside the duty cycle, the metal fuel cell is positively boosted and the cell is discharged. The frequency, voltage and duty ratio of the pulse voltage are determined by the relevant factors such as the area of a battery polar plate, the distance of the polar plate, the concentration of electrolyte and the like. Of course, the timing may be used to control the length of the loading pulse in some simple systems.
In the discharge process of the metal fuel cell, the anode electrode continuously loses electrons and separates out metal ions, and the metal ions can be gathered in the electrolyte and hydrolyzed to form charged colloidal particles. The colloidal particles formed by the metal ions are usually negative charge particles, so the colloidal particles are slowly accumulated on the anode electrode and slowly adsorbed on the surface of the anode electrode, and the polarization resistance of the anode electrode is increased; further, as the concentration of the colloidal particles in the electrolyte increases, the ion transport speed is also affected, thereby increasing the ion transport resistance of the electrolyte.
reverse pulse voltage is applied to the metal fuel cell in a discharging state, the electric field in the cell is intermittently changed through the reverse pulse voltage, colloid particles intermittently migrate along with the change of the internal electric field, vibration of the colloid particles between electrodes is caused, the colloid particles can be peeled off from the surfaces of the electrodes, the colloid particles can also vibrate in electrolyte under the action of the reverse pulse voltage, coagulation is caused, and therefore the electrodes are protected.
2. When the metal fuel cell is in the off-load state, applying a reverse rated voltage V to the metal fuel cellForehead (forehead)Said reverse rated voltage VForehead (forehead)Is greater than the discharge voltage V of the metal fuel cellPutThe voltage value of (2). Preferably, the reverse rated voltage VForehead (forehead)The static voltage of (A) is 0.9V-3V.
For example, a reverse rated voltage is applied to an electrode of a metal fuel cell in a load disconnected state, a discharge voltage value of the metal fuel cell is determined by an electrode material, and the reverse rated voltage V isForehead (forehead)slightly higher than the discharge voltage V of the metal fuel cellPutwhen the method is used, a small current opposite to the discharge current direction is formed between the electrodes in the battery, so that the internal electric field of the battery is changed, the anode protection is realized, and the condition that the oxidation layer of the anode electrode is too thick to inhibit the starting of the battery is avoided.
In addition, after the reverse rated voltage is applied for a certain time, the metal fuel cell is started to carry out one or more times of discharge for recovery, the electrode is activated, and the thickness of an oxide layer on the surface of the anode electrode is reduced, so that the aim of inhibiting the corrosion of the anode electrode in a static state is fulfilled.
Next, to verify the above two cases, the experimental process is as follows:
1. Applying reverse pulse voltage to metal fuel cell in discharge state to load
Environment: the weight of the anode aluminum alloy electrode is 18.32g, the effective area is 10 square centimeters, the effective area of the electrode is 10 square centimeters, the thickness is 0.6cm, and the maximum current density is as follows: 120-160 mA/square centimeter.
The test mode is as follows: preparing two brand-new finished products; the two products are loaded with a load 80MA and discharged in a current sharing mode, the voltage is 3.3V, and the discharge time is 10 hours every day; no. 1 does not use the electrode protection mechanism, and free discharge is carried out, and No. 2 uses the electrode protection mechanism.
Wherein daily weight consumption: (initial weight-end weight)/days spent
2. Applying reverse rated voltage to electrode of metal fuel cell in load disconnection state
Environment: the weight of the anode aluminum alloy electrode is 18.32g, the effective area is 10 square centimeters, the effective area of the electrode is 10 square centimeters, the thickness is 0.6cm, and the maximum current density is as follows: 120-160 mA/square centimeter.
Equipment: electronic load meter, internal resistance digital tester and bidirectional DCDC control panel set
Conditions are as follows: the battery is output under the state of constant voltage 1V, the triggering time is 1 hour, the triggering holding time is 5S, and the recovery time is detected for 2 minutes.
Testing the internal resistance change;
Serial number Time of day Voltage of Electric current Internal resistance of Area of polar plate Current density Open circuit voltage
1 detection 2:12 1V 430mA 528mR 10cm2 43mA 1.22704V
2 triggering 3.06 1V 400mA 570mR 10cm2 40mA 1.228V
3 recovery 3:08 1V 433mA 530mR 10cm2 43.3mA 1.22949V
4 triggering 4:06 1V 391mA 580mR 10cm2 39.1mA 1.22678V
5 recovery 4:08 1V 420mA 540mR 10cm2 42mA 1.2268V
6 triggering 5:06 1V 400mA 550mR 10cm2 40mA 1.22V
7 recovery 5:08 1V 420mA 540mR 10cm2 42mA 1.2268V
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by the present specification, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.

Claims (7)

1. A method of protecting an electrode of a metal fuel cell, comprising the steps of:
Applying a reverse voltage to the metal fuel cell, wherein the direction of the reverse voltage is opposite to the discharge direction of the metal fuel cell.
2. The electrode protection method for a metal fuel cell according to claim 1, wherein a reverse pulse voltage V is applied to the metal fuel cell when the metal fuel cell is in a discharge state to a loadPulseSaid reverse pulse voltage VPulseIs greater than the discharge voltage V of the metal fuel cellPutThe voltage value of (2).
3. The electrode protection method for a metal fuel cell according to claim 2, wherein the reverse pulse voltage V isPulseThe effective voltage of the middle duty ratio is 0.9V-3V.
4. The electrode protection method for a metal fuel cell according to claim 1, wherein a reverse rated voltage V is applied to the metal fuel cell when the metal fuel cell is in an off-load stateForehead (forehead)Said reverse rated voltage VForehead (forehead)Is greater than the discharge voltage V of the metal fuel cellPutThe voltage value of (2).
5. The method for protecting an electrode of a metal fuel cell according to claim 4, wherein the metal fuel cell is started up to perform one or more discharges after a reverse rated voltage is applied to the metal fuel cell for a certain period of time.
6. The electrode protection method for a metal fuel cell according to claim 4, whereinthe reverse rated voltage VForehead (forehead)The static voltage of (A) is 0.9V-3V.
7. The electrode protection method of a metal fuel cell according to claim 1, further comprising, before the step of applying a reverse voltage to the metal fuel cell, the reverse voltage being opposite to a discharge voltage of the metal fuel cell, the step of:
And detecting the internal resistance of the metal fuel cell, judging whether the internal resistance is greater than a trigger value, and if so, executing the step of applying reverse voltage to the metal fuel cell.
CN201910867847.2A 2019-09-15 2019-09-15 Electrode protection method for metal fuel cell Active CN110556554B (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020127466A1 (en) * 2001-02-28 2002-09-12 Ovshinsky Stanford R. Method of fuel cell activation
CN1508897A (en) * 2002-10-31 2004-06-30 ���µ�����ҵ��ʽ���� Fuel cell and working method of fuel cell system, and fuel cell system
CN101682062A (en) * 2007-06-14 2010-03-24 佳能株式会社 Fuel cell system and activation method for fuel cell
CN104600339A (en) * 2013-10-31 2015-05-06 现代自动车株式会社 Method for recovering fuel cell performance by using electrode reversal
CN105990615A (en) * 2015-02-14 2016-10-05 上海西胜电子科技有限公司 Intelligent regeneration and restoration method of industrial storage battery
CN106340688A (en) * 2016-08-31 2017-01-18 海赛普新能源高科技（江苏）有限公司 Method for life extension, repair, electric energy recovery of lead-acid batteries
CN108432016A (en) * 2015-12-25 2018-08-21 日产自动车株式会社 Fuel cell system and its control method

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020127466A1 (en) * 2001-02-28 2002-09-12 Ovshinsky Stanford R. Method of fuel cell activation
CN1508897A (en) * 2002-10-31 2004-06-30 ���µ�����ҵ��ʽ���� Fuel cell and working method of fuel cell system, and fuel cell system
CN101682062A (en) * 2007-06-14 2010-03-24 佳能株式会社 Fuel cell system and activation method for fuel cell
CN104600339A (en) * 2013-10-31 2015-05-06 现代自动车株式会社 Method for recovering fuel cell performance by using electrode reversal
CN105990615A (en) * 2015-02-14 2016-10-05 上海西胜电子科技有限公司 Intelligent regeneration and restoration method of industrial storage battery
CN108432016A (en) * 2015-12-25 2018-08-21 日产自动车株式会社 Fuel cell system and its control method
CN106340688A (en) * 2016-08-31 2017-01-18 海赛普新能源高科技（江苏）有限公司 Method for life extension, repair, electric energy recovery of lead-acid batteries

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