CN113871668A - Reversible battery system and method based on hydrogen peroxide electrochemical cycle - Google Patents
Reversible battery system and method based on hydrogen peroxide electrochemical cycle Download PDFInfo
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- CN113871668A CN113871668A CN202111123206.XA CN202111123206A CN113871668A CN 113871668 A CN113871668 A CN 113871668A CN 202111123206 A CN202111123206 A CN 202111123206A CN 113871668 A CN113871668 A CN 113871668A
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- hydrogen
- oxygen
- hydrogen peroxide
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 363
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- 238000000034 method Methods 0.000 title claims abstract description 25
- 239000001301 oxygen Substances 0.000 claims abstract description 321
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 321
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 312
- 239000001257 hydrogen Substances 0.000 claims abstract description 183
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 183
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 182
- 239000003792 electrolyte Substances 0.000 claims abstract description 118
- 239000003054 catalyst Substances 0.000 claims abstract description 111
- 238000003860 storage Methods 0.000 claims abstract description 103
- 239000012528 membrane Substances 0.000 claims abstract description 97
- 238000007600 charging Methods 0.000 claims abstract description 88
- 238000006243 chemical reaction Methods 0.000 claims abstract description 71
- 238000007599 discharging Methods 0.000 claims abstract description 38
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 9
- 230000003647 oxidation Effects 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 44
- 239000003575 carbonaceous material Substances 0.000 claims description 39
- 239000007788 liquid Substances 0.000 claims description 27
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 26
- 238000000926 separation method Methods 0.000 claims description 25
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Images
Classifications
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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
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
- H01M8/0656—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants by electrochemical means
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
- H01M4/8668—Binders
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9008—Organic or organo-metallic compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
-
- 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
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0213—Gas-impermeable carbon-containing materials
-
- 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
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
- H01M8/0234—Carbonaceous material
-
- 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 a reversible battery system and a method based on hydrogen peroxide electrochemical circulation, wherein the system comprises: the hydrogen storage device comprises an electrolyte membrane structure battery module, a hydrogen circulation storage module, an oxygen circulation storage module, a hydrogen peroxide circulation storage module and a power conversion module, wherein the hydrogen circulation storage module, the oxygen circulation storage module and the hydrogen peroxide circulation storage module are respectively communicated with the electrolyte membrane structure battery module; the electrolyte membrane structure cell module includes an oxygen electrode chamber containing an oxygen electrode and an oxygen electrode catalyst layer; a hydrogen electrode chamber containing a hydrogen electrode and a hydrogen electrode catalyst layer; and an electrolyte membrane; the power supply conversion module can switch the system into a charging mode or a discharging mode; the oxygen electrode catalyst layer can catalyze hydrogen peroxide oxidation to generate oxygen in a charging mode; or catalyze the two-electron oxygen reduction to produce hydrogen peroxide in a discharge mode. The system can realize the storage and conversion of energy with higher energy conversion efficiency and higher system stability through the continuous charging and discharging operation of the battery.
Description
Technical Field
The invention relates to the technical field of reversible batteries, in particular to a reversible battery system and a method based on hydrogen peroxide electrochemical circulation.
Background
The traditional reversible hydrogen-oxygen fuel cell is an electrochemical charging and discharging device which combines the water electrolysis hydrogen production technology and the hydrogen-oxygen fuel cell power generation technology. The reversible hydrogen-oxygen fuel cell can electrolyze water into hydrogen and oxygen and collect and store the hydrogen and the oxygen in a charging mode (or called as an electrolytic water mode), and realizes the conversion of electric energy into chemical energy (hydrogen energy) (oxygen electrode generation electrochemistry 4 e)-Water oxidation oxygen evolution reaction: 2H2O→4H++4e-+O2Or 4OH-→O2+2H2O+4e-(ii) a RHE, the theoretical potential is 1.23V vs, and RHE is the potential of a reversible hydrogen electrode; the hydrogen electrode generates electrochemical hydrogen evolution reaction: 2H++2e-→H2Or 2H2O+2e-→H2+2OH-(ii) a Rhe) theoretical potential 0V vs); in the discharging mode (or called oxyhydrogen fuel cell mode), the stored hydrogen and oxygen or air can be used for carrying out electrochemical reaction to generate water, and simultaneously electric energy is released, so that the conversion from chemical energy (hydrogen energy) to electric energy is realized (electrochemical four-electron oxygen reduction reaction is carried out on an oxygen electrode: 4H++4e-+O2→2H2O or O2+2H2O+4e-→4OH-Theoretical potential 1.23V vs. rhe; the hydrogen electrode generates electrochemical oxidation reaction of hydrogen: h2→2H++2e-Or H2+2OH-→-2H2O+2e-Rhe, theoretical potential 0V vs).
The conventional reversible hydrogen-oxygen fuel cell as a clean energy storage system has the following main problems in the application process: (1) the theoretical potential of the oxygen electrode reaction is too high (1.23V vs. RHE), so that a titanium-based diffusion layer, a gold-plated runner plate and a bipolar plate which are resistant to electrochemical corrosion need to be used, and the material cost is high; (2) the dynamic process of the four-electron oxygen reduction reaction and the electrocatalytic water oxidation oxygen evolution reaction on the oxygen electrode is slow, the overpotential is large (the overpotential is the absolute value of the difference value between the working potential and the theoretical potential), the system energy conversion efficiency is low, and a large amount of noble metal-based catalysts are needed for catalytic reaction; (3) the high potential of the oxygen electrode has great damage to the catalyst, the gas diffusion layer, the membrane material, the bipolar plate and the like, and the system stability is poor.
In order to realize the energy storage and conversion functions of the reversible fuel cell more stably and efficiently, improve the energy conversion efficiency in the charging and discharging process, reduce the cost of cell materials and improve the system stability, a reaction system needs to be found in principle, and the theoretical potential and the overpotential of the oxygen electrode electrochemical reaction in two modes are reduced.
Disclosure of Invention
In order to solve the above problems, an object of the present invention is to provide a reversible battery system and method based on hydrogen peroxide electrochemical cycle, which can realize storage and conversion of electric energy, and realize storage and conversion of energy with higher energy conversion efficiency and higher system stability through continuous charging and discharging operations of a battery.
In order to achieve the above object, the technical solution of the present invention is as follows.
A reversible battery system based on hydrogen peroxide electrochemical cycling, comprising: the hydrogen storage system comprises an electrolyte membrane structure battery module, a hydrogen circulating storage module, an oxygen circulating storage module, a hydrogen peroxide circulating storage module and a power supply conversion module;
the electrolyte membrane structure cell module includes:
the hydrogen electrode chamber is provided with a hydrogen gas inlet and a hydrogen gas outlet; the hydrogen circulation storage module is respectively communicated with the hydrogen inlet and the hydrogen outlet; a hydrogen electrode and a hydrogen electrode catalyst layer are arranged in the hydrogen electrode chamber;
the oxygen electrode chamber is provided with an oxygen electrode chamber inlet and an oxygen electrode chamber outlet; the oxygen electrode chamber inlet is respectively communicated with the oxygen circulating storage module and the hydrogen peroxide circulating storage module; an oxygen electrode gas-liquid separation module is connected to an outlet of the oxygen electrode chamber, the oxygen electrode gas-liquid separation module is respectively communicated with the oxygen circulating storage module and the hydrogen peroxide circulating storage module, and an oxygen electrode catalyst layer are arranged in the oxygen electrode chamber;
the electrolyte membrane is arranged between the hydrogen electrode chamber and the oxygen electrode chamber and is used for separating the oxygen electrode chamber from the hydrogen electrode chamber;
the power supply conversion module is respectively connected with the hydrogen electrode and the oxygen electrode, and can switch the working mode of the electrolyte membrane structure battery module into a charging mode or a discharging mode;
when the working mode of the electrolyte membrane structure battery module is a charging mode, the oxygen electrode catalyst layer can catalyze the oxidation of hydrogen peroxide in the oxygen electrode chamber to generate oxygen;
when the working mode of the electrolyte membrane structure battery module is a discharging mode, the oxygen electrode catalyst layer can catalyze the two-electron oxygen in the oxygen electrode chamber to reduce and generate hydrogen peroxide.
The power supply conversion module is used for switching the working mode of the electrolyte membrane structure battery module into a charging mode or a discharging mode, is connected with an external power supply in the charging mode, and is connected with external electric equipment or power supply storage equipment in the discharging mode. The hydrogen electrode and the oxygen electrode are respectively connected with an external power supply, external electric equipment or power supply storage equipment through the power supply conversion module. In the discharge mode, only oxygen is introduced into the oxygen electrode chamber, and the oxygen electrode chamber generates oxygen reduction reaction of two electrons to generate hydrogen peroxide.
Further, the electrolyte membrane is capable of blocking hydrogen peroxide within the oxygen electrode chamber; the electrolyte membrane is a composite membrane of any one or more of a proton exchange membrane, an anion exchange membrane, a hydroxyl ion exchange membrane and a solid electrolyte membrane.
Further, the hydrogen circulation storage module is used for collecting and storing hydrogen in a charging mode or conveying and circulating hydrogen in a discharging mode of the system;
the oxygen circulation storage module is used for collecting and storing oxygen in a charging mode of the system or conveying and circulating oxygen or air in a discharging mode;
the hydrogen peroxide circulating storage module is used for conveying and circulating hydrogen peroxide electrolyte in a charging mode or collecting and storing hydrogen peroxide electrolyte in a discharging mode.
Furthermore, the hydrogen peroxide circulating storage module comprises a hydrogen peroxide electrolyte storage tank and a circulating pump, and the hydrogen peroxide electrolyte storage tank is communicated with the oxygen electrode chamber inlet through the circulating pump.
Further, the oxygen electrode gas-liquid separation module comprises a gas-liquid separation device, and is used for carrying out gas-liquid separation on the hydrogen peroxide electrolyte and the oxygen output from the oxygen electrode chamber outlet, storing the separated hydrogen peroxide electrolyte into the hydrogen peroxide circulating storage module, and storing the separated oxygen into the oxygen circulating storage module.
Further, the hydrogen electrode catalyst layer is composed of a Pt/C catalyst, a binder and a gas diffusion layer;
the oxygen electrode catalyst layer is composed of an oxygen electrode catalyst material, a binder and a gas diffusion layer;
the oxygen electrode catalyst material is any one of a metal alloy material, a metal nitrogen co-doped carbon material, an organic metal complex and a metal ion doped polymer.
Further preferably, the metal alloy material is any one of platinum amalgam, palladium amalgam, gold-palladium alloy, copper amalgam and silver-mercury alloy. The metal nitrogen-codoped carbon material is a platinum nitrogen-codoped carbon material, a palladium nitrogen-codoped carbon material, a cobalt nitrogen-codoped carbon material, an iron nitrogen-codoped carbon material, a manganese nitrogen-codoped carbon material, a copper nitrogen-codoped carbon material, an iron-manganese nitrogen-codoped carbon material and an iron-cobalt nitrogen-codoped carbon material. The organic metal complex is porphyrin metal complex, bipyridine metal complex and polypyridine polydentate chelating metal complexAny one of dipyrrole metal complexes, polypyrrole chelate metal complexes and 2, 2' -dipyridine amine metal complexes; wherein the metal complex ion of the organometallic complex is Fe2+、Fe3+、Co2+、Co3+、Cu2+、Mn2+、Pt2+、Pd2+Any one of them. The metal ion doped polymer is iron-doped polypyrrole, cobalt-doped polypyrrole, manganese-doped polypyrrole, copper-doped polypyrrole, platinum-doped polypyrrole and palladium-doped polypyrrole; iron-doped polypyridine, cobalt-doped polypyridine, manganese-doped polypyridine, copper-doped polypyridine, platinum-doped polypyridine, palladium-doped polypyridine; iron-doped polyaniline, cobalt-doped polyaniline, manganese-doped polyaniline, copper-doped polyaniline, platinum-doped polyaniline, and palladium-doped polyaniline.
The binder is one or a mixture of more of perfluorinated sulfonic acid polyelectrolyte (Nafion), sulfonated polyether ether ketone polyelectrolyte, sulfonated polysulfone polyelectrolyte, phosphorylated polybenzimidazole, quaternized polysulfone polyelectrolyte, polybenzimidazole polyelectrolyte, polyvinyl alcohol polyelectrolyte, heteropoly acid electrolyte and polytetrafluoroethylene.
It is noted that the hydrogen peroxide electrochemical cycle based reversible cell system capable of achieving energy storage and conversion at low voltage (0.7V) also depends on the oxygen electrode catalyst material in the electrolyte membrane structure cell module. The oxygen electrode catalyst material is a catalyst material which has the activity of catalyzing two-electron oxygen to be reduced to generate hydrogen peroxide and the activity of catalyzing hydrogen peroxide to be oxidized to generate oxygen.
The invention also provides a charging and discharging method of the reversible battery system based on hydrogen peroxide electrochemical cycle, when the reversible battery system runs in a charging mode, the method comprises the following steps:
s101, introducing a hydrogen peroxide electrolyte in the hydrogen peroxide circulating storage module into the oxygen electrode chamber;
s102, the hydrogen peroxide circulating storage module is communicated with an external power supply through the power supply conversion module, the external power supply applies voltage between the oxygen electrode and the hydrogen electrode, so that hydrogen peroxide in the oxygen electrode chamber is converted into oxygen under the action of the oxygen electrode catalyst layer, and the hydrogen electrode chamber generates electrochemical hydrogen evolution reaction to generate hydrogen;
specifically, the hydrogen electrode chamber and the oxygen electrode chamber respectively react as follows:
an oxygen electrode chamber: h in acidic or neutral environment2O2→2H++2e-+O2Theoretical potential 0.7V vs. rhe; or HO in alkaline environment2 -+OH-→O2+H2O+2e-(ii) a Hydrogen peroxide in the form of hydrogen peroxide ions HO in the presence of an alkali2 -The form exists; hydrogen electrode chamber: acidic or neutral 2H++2e-→H2Or basic 2H2O+2e-→H2+2OH-(ii) a Rhe at theoretical potential 0V vs;
s103, collecting and storing the hydrogen generated in the hydrogen electrode chamber in the hydrogen circulation storage module, and separating and collecting the oxygen generated in the oxygen electrode chamber in the oxygen circulation storage module.
Or when the reversible battery system is operated in a discharge mode, the method is as follows:
s201, the hydrogen peroxide circulating storage module is communicated with external power equipment or power storage equipment through a power conversion module; then introducing the hydrogen in the hydrogen circulation storage module into the hydrogen electrode chamber, and introducing the oxygen or air in the oxygen circulation storage module into the oxygen electrode chamber;
s202, hydrogen electrochemical oxidation reaction occurs in the hydrogen electrode chamber, two-electron oxygen reduction reaction occurs in the oxygen electrode chamber to generate hydrogen peroxide, and voltage and current are output;
specifically, the oxygen electrode chamber and the hydrogen electrode chamber respectively react as follows:
an oxygen electrode chamber: o in acidic or neutral environment2+2e-+2H+→H2O2Or O in an alkaline environment2+H2O+2e-→HO2 -+OH-(ii) a Theory of the inventionPotential 0.7V vs. rhe; hydrogen electrode chamber: h in acidic or neutral environment2→2H++2e-Or H in an alkaline environment2+2OH-→2H2O+2e-(ii) a Rhe at theoretical potential 0V vs;
s203, the oxygen electrode gas-liquid separation module separates and collects the oxygen and the hydrogen peroxide solution output by the oxygen electrode chamber.
Further, in S101, the flow rate of the hydrogen peroxide electrolyte introduced into the oxygen electrode chamber is 10-300 mL/min; the concentration of the hydrogen peroxide electrolyte is 0.1-90 wt%; the pH value of the hydrogen peroxide electrolyte is-3-17; in S102, in a charging mode, the electrolysis temperature of the electrolyte membrane structure battery module is 10-80 ℃; the voltage applied between the oxygen electrode and the hydrogen electrode by the external power supply is 0.7V-1V.
Further, in S201, the flow rate of hydrogen, oxygen or air is 0.05L/min to 1.00L/min; in S202, in a discharging mode, the reaction temperature of the electrolyte membrane structure battery module is 10-80 ℃, and the discharging voltage is 0V-0.8V; wherein, the discharge voltage 0V means that the discharge is performed at 0V vs. rhe, and the reaction still proceeds; in S203, the concentration of the hydrogen peroxide solution is 0.1-90 wt%. It should be noted that the oxygen electrode chamber can be fed with oxygen or air, wherein the oxygen content in the air is sufficient to support the normal operation of the reaction, and the investment cost is reduced.
The invention has the beneficial effects that:
1. the invention provides a novel energy storage and conversion method, which utilizes the electrochemical cycle reaction of hydrogen peroxide to ensure that a battery system has a discharging function and a charging function.
2. The system and the method can realize energy conversion at a lower initial working voltage of 0.7V, the initial working voltage is close to the thermodynamic theoretical voltage, the energy conversion efficiency is over 90 percent near the initial working voltage, and the system and the method have extremely high energy conversion efficiency.
3. The oxygen electrode catalyst, the oxygen electrode gas diffusion layer and the oxygen electrode flow channel plate in the device can all use cheap carbon-based materials, and replace expensive metal catalysts, titanium metal diffusion layers, gold-plated metal flow channel plates and bipolar plates used by the oxygen electrode of the traditional reversible fuel cell device, so that the material cost of the system is reduced.
4. The core content of the invention is that the electrochemical cycle reaction of hydrogen peroxide replaces the oxyhydrogen-water electrochemical cycle reaction in the traditional reversible fuel cell; by using the oxygen electrode catalyst material, the electrochemical cycle and the charge-discharge process of the hydrogen peroxide can be realized under extremely high energy conversion efficiency, and the system stability is high.
Drawings
Fig. 1 is a schematic diagram of a reversible battery system based on hydrogen peroxide electrochemical cycle according to embodiment 1 of the present invention.
Fig. 2 is a schematic view illustrating the operation of the electrolyte membrane structure cell module in the reversible cell system shown in fig. 1 in a charge mode and a discharge mode.
Fig. 3 is an assembly view showing the components in the electrolyte membrane structured cell module of example 1 of the invention.
Fig. 4 is a graph of (a) a discharge voltage-current density curve and (b) a voltage-hydrogen peroxide generation rate dispersion when the reversible battery system of example 1 is operated in a discharge mode.
Fig. 5 is a graph of (a) a charging voltage-current density curve and (b) a charging voltage-hydrogen generation rate dispersion when the reversible battery system of example 1 is operated in a charging mode.
Fig. 6 is a graph of (a) a current density-voltage curve at 10 times of switching operation and (b) a time-current density curve at the switching operation of the reversible battery system of example 1 in the charge mode and the discharge mode.
Fig. 7(a) is a graph of charging current density versus voltage for electrolytes of different pH when the reversible battery system of example 2 is operated in the charging mode.
Fig. 7(b) is a graph of charging current density versus voltage for different hydrogen peroxide concentrations when the reversible battery system of example 3 was operated in the charging mode.
Fig. 7(c) is a discharge current density-voltage graph for different air flow rates when the reversible battery system of example 4 is operated in the discharge mode.
Fig. 7(d) is a discharge current density-voltage graph of the reversible battery system of example 5 at different operating temperatures when the system is operated in the discharge mode.
Fig. 8 is a voltage-current density comparison curve of the reversible cell system described in example 1 of the present invention and the conventional reversible fuel cells of comparative examples 1 and 2 in charge and discharge modes.
Fig. 9 is a voltage-current density comparison curve of the oxygen electrode catalyst used in the reversible cell system of the present invention in example 1 and the commercial Pt/C catalyst used in the reversible cell system of the present invention in comparative example 3 in charge and discharge modes.
The notation in the figure is: 1-an electrolyte membrane structure cell module; 2-a power conversion module; 3-a hydrogen circulating storage module; 4-hydrogen inlet; 5-hydrogen gas outlet; 6-hydrogen peroxide circulating storage module; 7-oxygen electrode chamber inlet; 8-oxygen electrode chamber outlet; 9-oxygen electrode gas-liquid separation module; 10-oxygen outlet; 11-a hydrogen peroxide outlet; 12-an oxygen circulating storage module; 13-an oxygen recycle line; 14-a hydrogen peroxide recycle line; 15-hydrogen recycle line.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
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.
Example 1
Fig. 1 is a schematic diagram of a reversible battery system based on hydrogen peroxide electrochemical cycle according to an embodiment of the present invention. The reversible battery system comprises an electrolyte membrane structure battery module 1, a hydrogen circulation storage module 3, an oxygen circulation storage module 12, a hydrogen peroxide circulation storage module 6, an oxygen electrode gas-liquid separation module 9 and a power supply conversion module 2, wherein the hydrogen circulation storage module 3, the oxygen circulation storage module 12, the hydrogen peroxide circulation storage module 6, the oxygen electrode gas-liquid separation module 9 and the power supply conversion module 2 are respectively communicated with the electrolyte membrane structure battery module 1.
The electrolyte membrane structure battery module 1 includes an oxygen electrode chamber containing an oxygen electrode and an oxygen electrode catalyst layer and a flow channel plate, a hydrogen electrode chamber containing a hydrogen electrode and a hydrogen electrode catalyst layer and a flow channel plate, and an electrolyte membrane that blocks the oxygen electrode chamber and the hydrogen electrode chamber. The working temperature of the electrolyte membrane structure battery module can be 10-80 ℃.
The power conversion module 2 is respectively connected with the oxygen electrode and the hydrogen electrode, and the power conversion module 2 can switch the working mode of the electrolyte membrane structure battery module 1 into a charging mode or a discharging mode, and is connected with an external power supply in the charging mode or is connected with external electric equipment or power storage equipment in the discharging mode. When the working mode of the electrolyte membrane structure battery module is a charging mode, the oxygen electrode catalyst layer can catalyze the oxidation of hydrogen peroxide in the oxygen electrode chamber to generate oxygen; when the operation mode of the electrolyte membrane structure cell module is a discharge mode, the oxygen electrode catalyst layer can catalyze the two-electron oxygen in the oxygen electrode chamber to reduce and generate hydrogen peroxide.
Referring to fig. 1 and 2, a hydrogen inlet 4 and a hydrogen outlet 5 are disposed on the hydrogen electrode chamber of the electrolyte membrane structure battery module 1, and the hydrogen inlet 4 and the hydrogen outlet 5 are respectively connected to an outlet and an inlet of the hydrogen circulation storage module 3 through a hydrogen circulation pipeline 15. An oxygen electrode chamber inlet 7 and an oxygen electrode chamber outlet 8 are arranged on an oxygen electrode chamber of the electrolyte membrane structure battery module 1, an oxygen circulating storage module 12 is connected with the oxygen electrode chamber inlet 7 through an oxygen circulating pipeline 13, a hydrogen peroxide circulating storage module 6 is connected with the oxygen electrode chamber inlet 7 through a hydrogen peroxide circulating pipeline 14, the oxygen electrode chamber outlet 8 is connected with an oxygen electrode gas-liquid separation module 9 through a pipeline, an oxygen gas outlet 10 and a hydrogen peroxide liquid outlet 11 are arranged on the oxygen electrode gas-liquid separation module 9, the oxygen gas outlet 10 of the oxygen electrode gas-liquid separation module 9 is connected with the oxygen circulating storage module 12 through an oxygen circulating pipeline, and the oxygen electrode gas-liquid separation module 9 and the hydrogen peroxide liquid outlet 11 are connected with the hydrogen peroxide circulating storage module 6 through a hydrogen peroxide circulating pipeline 14.
When the device is used, in a charging mode, the hydrogen peroxide circulating storage module 6 leads hydrogen peroxide electrolyte into the oxygen electrode chamber inlet 7 through the hydrogen peroxide circulating pipeline 14, and the power conversion module 2 is connected with an external power supply and applies voltage to the electrolyte membrane structure battery module 1 to generate current; the oxygen electrode generates hydrogen peroxide electrochemical oxidation reaction to generate oxygen, the generated oxygen and residual hydrogen peroxide electrolyte enter an oxygen electrode gas-liquid separation module 9 from an oxygen electrode chamber outlet 8, the separated oxygen is introduced into an oxygen circulating storage module 12 through an oxygen circulating pipeline 13, and the separated residual hydrogen peroxide electrolyte is introduced into a hydrogen peroxide circulating storage module 6 through a hydrogen peroxide circulating pipeline 14; the hydrogen electrode generates electrochemical hydrogen evolution reaction to generate hydrogen, and the generated hydrogen enters the hydrogen circulation storage module 3 through the hydrogen outlet 5 and the hydrogen circulation pipeline 15.
In the discharging mode, the hydrogen circulation storage module 3 is communicated with the hydrogen electrode chamber through a hydrogen circulation pipeline 15 and a hydrogen inlet 4 and a hydrogen outlet 5 of the electrolyte membrane structure battery module, and circularly inputs hydrogen to the hydrogen electrode chamber; the oxygen circulation storage module 12 inputs oxygen (or air) to the oxygen electrode chamber through an oxygen circulation pipeline 13 and the oxygen electrode chamber inlet 7; the hydrogen electrode chamber of the electrolyte membrane structure battery module 1 generates hydrogen electrochemical oxidation reaction, the oxygen electrode chamber generates two-electron oxygen reduction reaction to generate hydrogen peroxide, and voltage and current are output; the electrolyte membrane structure battery module 1 outputs electric power to external electric equipment or power storage equipment through the power conversion module 2; hydrogen peroxide generated by the oxygen electrode chamber enters the oxygen electrode gas-liquid separation module 9 through an oxygen electrode chamber outlet 8 for separation, and the separated gas enters the oxygen circulating storage module 12 through an oxygen circulating pipeline 13; the separated hydrogen peroxide solution enters the hydrogen peroxide circulation module 6 through the hydrogen peroxide circulation pipeline 14 for storage.
The reversible battery system realizes the storage and release of electric energy by utilizing the electrochemical cycle reaction of hydrogen peroxide. In the charging mode of the battery system, the oxygen electrode generates hydrogen peroxide electrochemical oxidation reaction and generates oxygen; the hydrogen electrode generates electrochemical hydrogen evolution reaction and generates hydrogen, so that electric energy is converted into chemical energy (hydrogen and oxygen) and stored; in the discharge mode, the oxygen generates electrochemical two-electron oxygen reduction reaction in the oxygen electrode chamber to generate hydrogen peroxide, the hydrogen electrode chamber generates electrochemical hydrogen oxidation reaction, and electric energy is output externally.
As a novel energy storage and conversion technology, the reversible battery system based on hydrogen peroxide electrochemical cycle realizes the functions of hydrogen production by hydrogen peroxide electrolysis and discharge of a hydrogen-oxygen fuel cell in the same system, reduces the volume of the system and greatly reduces the overall cost of the system. The hydrogen peroxide electrochemical circulating battery utilizes a specific oxygen electrode catalyst to catalyze the electrochemical oxidation and two-electron oxygen reduction reaction of hydrogen peroxide near 0.7V potential, is smaller than the electrochemical oxidation oxygen evolution and four-electron oxygen reduction reaction potential (1.23V) of water in the traditional reversible fuel battery, can effectively reduce the working potential of an oxygen electrode, further avoids the electrochemical oxidation of an oxygen electrode material, and improves the stability of a system. The hydrogen peroxide electrochemical cycle battery can enable the system to work near a theoretical voltage (0.7V) by using a proper electrode catalyst material, and the charge-discharge energy conversion efficiency of the system is improved. In addition, the hydrogen peroxide electrochemical cycle battery system realizes the quick output of electric energy in high power demand through the efficient switching between the charging mode and the discharging mode, and the electric energy is efficiently transferred to hydrogen energy in low power demand.
The reversible battery system based on electrochemical cycling of hydrogen peroxide described above is described in further detail below. Wherein the hydrogen electrode catalyst layer is composed of a Pt/C catalyst, a binder and a gas diffusion layer; the oxygen electrode catalyst layer is composed of an oxygen electrode catalyst material, a binder and a gas diffusion layer.
Fig. 3 is a schematic view showing the assembly of each element in the electrolyte membrane structured cell module according to the embodiment of the invention. The oxygen electrode catalyst material is a cobalt-nitrogen co-doped carbon-based material, and the oxygen electrode diffusion layer is carbon cloth; the oxygen electrode flow channel plate is a graphite flow channel plate, and the oxygen electrode collector plate is a graphite collector plate. The hydrogen electrode catalyst is 20 wt% commercial Pt/C catalyst, the hydrogen electrode diffusion layer is carbon paper, the hydrogen electrode runner plate is a graphite runner plate, and the hydrogen electrode collector plate is a graphite collector plate. The adhesive is commercial perfluorosulfonic acid (Nafion) adhesive, the electrolyte membrane is commercial proton exchange membrane Nafion N-211, and the sealing ring is fiber reinforced polytetrafluoroethylene membrane.
The assembly steps of the above electrolyte membrane structure cell module are as follows:
(1) preparation of oxygen electrode catalyst material: 11mmol of aniline, 55mmol of cobalt chloride and 0.2g of commercial activated carbon were uniformly mixed into a 1M hydrochloric acid solution, and the slurry after concentration of the solution was subjected to high-temperature heat treatment at 900 ℃ for 1 hour in a nitrogen atmosphere to obtain an initial sample. The initial sample was immersed in concentrated hydrochloric acid for 24 hours and then subjected to high-temperature pyrolysis again at 900 ℃ in a nitrogen atmosphere to obtain a cobalt-nitrogen co-doped carbon-based material.
(2) Preparation of oxygen electrode catalyst layer: the cobalt-nitrogen co-doped carbon-based material and a binder (5 wt% Nafion) are mixed according to a mass ratio of 2: 1, dispersing into a mixed solution of isopropanol and deionized water, spraying the mixed dispersion liquid uniformly and coating the mixed dispersion liquid on a 4cm thick film2Carbon cloth with a loading of 2mg/cm2；
(3) Preparation of Pt/C catalyst layer: commercial 20 wt% Pt/C catalyst and binder (5 wt% Nafion) are dispersed into a mixed solution of isopropanol and deionized water according to the mass ratio of 7:3, and the mixed dispersion solution is sprayed on 4cm2The loading amount on the carbon paper layer is 0.20mg/cm2；
(4) Assembling the electrolyte membrane structure cell: the hydrogen electrode catalyst layer, the oxygen electrode catalyst layer, the proton exchange membrane (Nafion N-211), and the cell holder were assembled in the manner of fig. 3.
The cell module with the electrolyte membrane structure is connected into a reversible cell system based on hydrogen peroxide electrochemical cycle according to the connection mode shown in figure 1, and a performance test is carried out, wherein the test process is as follows:
1. discharge mode performance test
And introducing the hydrogen of the hydrogen circulation storage module 3 into a hydrogen electrode chamber of the electrolyte membrane structure battery module 1, and introducing the oxygen of the oxygen circulation storage module 12 into an oxygen electrode chamber of the electrolyte membrane structure battery module 1, wherein the flow rate of the hydrogen and the oxygen is 0.50L/min, and the working temperature of the battery is 25 ℃. The external electric equipment was connected to the electrolyte membrane structured cell module 1 via the power conversion module 2, and the discharge voltage and current density data were recorded by a fuel cell station (Scribner 850e), as shown in fig. 4. The mixture of hydrogen peroxide and oxygen in the effluent is separated by the oxygen electrode gas-liquid separation module 9, the hydrogen peroxide solution is collected to the hydrogen peroxide circulating storage module 6, and the residual oxygen flows back to the oxygen circulating storage module 12.
Fig. 4(a) is a discharge voltage-current density curve of the reversible battery system when operating in a discharge mode. The data in fig. 4(a) show that the system is capable of generating a discharge current in the voltage range of 0.7V-0.2V in the discharge mode. The initial discharge voltage (or open circuit voltage) of the system is 0.7V. When the discharge voltage was reduced from 0.7V to 0.2V, the current density was gradually increased and reached 230mA/cm at 0.2V2。
Fig. 4(b) is a graph of voltage versus hydrogen peroxide generation rate data for the reversible battery system operating in a discharge mode. As indicated by the data in fig. 4(b), the system can generate hydrogen peroxide at a rate in the discharge mode. The hydrogen peroxide generation rate gradually increases with the decrease of the discharge voltage, and reaches 1.00mmol/cm at a voltage of about 0.3V2/h。
2. Charge mode performance test
Injecting 0.50mol/L sulfuric acid and 0.50mol/L hydrogen peroxide mixed electrolyte into an oxygen electrode chamber of the electrolyte membrane structure battery module 1 through the hydrogen peroxide circulating storage module 6; an external power source was turned on by the power switching module 2 to control the electrolyte membrane structured cell module 1, a charging voltage was applied to the electrolyte membrane structured cell module 1 in a voltage range of 0.7V to 1V, and a charging voltage-current density curve was recorded with an electrochemical workstation (energy lab XM), as shown in fig. 5 (a). The produced hydrogen gas was collected into the hydrogen circulation storage module 3 and the hydrogen generation rate was recorded as shown in fig. 5 (b). And introducing the generated oxygen and the electrolyte flowing out into the oxygen electrode gas-liquid separation module 9 for separation, introducing the separated oxygen into the oxygen circulating storage module 12 for storage, and introducing the separated hydrogen peroxide electrolyte into the hydrogen peroxide circulating storage module 6 for storage.
Fig. 5(a) is a charging voltage-current density curve of the reversible battery system when operating in a charging mode. The results in fig. 5(a) show that the system can generate current in the charging voltage range of 0.7V to 1.0V. As the charging voltage increases from 0.7V to 1.0V, the current density increases; the current density reaches about 250mA/cm at a charging voltage of 1.0V2。
Fig. 5(b) is a graph of charging voltage versus hydrogen generation rate data for the reversible battery system operating in a charging mode. As indicated by the data in fig. 5(b), the system can generate and store hydrogen gas in the hydrogen electrode chamber in the charging mode. As the charging voltage increases from 0.7V to 1.0V, the hydrogen generation rate increases. The hydrogen generation rate at 1.0V was 6mmol/cm2/h。
3. System cycling stability test
Switching the hydrogen peroxide electrochemical cycle battery system between a charging mode and a discharging mode, and recording a current density-voltage curve of cyclic operation between the charging mode and the discharging mode, as shown in fig. 6 (a); cycle run time-current density curve, as shown in fig. 6 (b).
Fig. 6(a) is a current density-voltage graph of the reversible battery system in 10 switching operations in the charge mode and the discharge mode. The data in fig. 6(a) shows that the system can achieve cyclic switching in both modes of operation and maintain stable performance. Fig. 6(b) is a time-current density curve when the reversible battery system is switched between the charge mode and the discharge mode. It is shown by the data in fig. 6(b) that the system can maintain stable charge-discharge cycle performance.
Example 2
The reversible battery system based on electrochemical cycle of hydrogen peroxide provided by the embodiment of the present invention is substantially the same as the reversible battery system of the embodiment 1, except that, when operating in the charging mode, the oxygen electrode chamber electrolyzes hydrogen peroxide to generate oxygen, and the reaction can be performed in acidic, neutral and alkaline systems. In order to study the battery performance of the system working in the charging mode under different pH conditions, embodiment 2 of the present invention tests the charging performance of the system under different pH conditions, specifically, the comparison conditions are as follows:
(1) one group of: the electrolyte membrane is a proton exchange membrane Nafion N-211, and the binder is Nafion. The electrolyte is a mixed solution of sulfuric acid and hydrogen peroxide, wherein the concentration of the sulfuric acid is 0.50mol/L, and the concentration of the hydrogen peroxide is 0.50 mol/L; the pH was 0.3. (2) Two groups are as follows: the electrolyte membrane is a proton exchange membrane Nafion N-211, and the binder is Nafion. The electrolyte is a mixed solution of sulfuric acid and hydrogen peroxide, wherein the concentration of the sulfuric acid is 0.001mol/L, and the concentration of the hydrogen peroxide is 0.50 mol/L; the pH was 3. (3) Three groups: the electrolyte membrane is a proton exchange membrane Nafion N-211, and the binder is Nafion. The electrolyte is a mixed solution of a phosphate buffer solution and hydrogen peroxide, wherein the concentration of the phosphate buffer solution is 1mol/L, and the concentration of the hydrogen peroxide is 0.5 mol/L; the pH was 7. (4) Four groups: the electrolyte membrane is an anionic membrane FAA-3-PK-130, and the binder is quaternary ammonium polysulfone polyelectrolyte. The electrolyte is a mixed solution of a potassium hydroxide solution and hydrogen peroxide, wherein the concentration of the potassium hydroxide solution is 0.0001mol/L, and the concentration of the hydrogen peroxide is 0.50 mol/L; the pH was 10. (5) Five groups are as follows: the electrolyte membrane is an anionic membrane FAA-3-PK-130, and the binder is quaternary ammonium polysulfone polyelectrolyte. The electrolyte is a mixed solution of a potassium hydroxide solution and hydrogen peroxide, wherein the concentration of the potassium hydroxide solution is 1.00mol/L, and the concentration of the hydrogen peroxide is 0.50 mol/L; the pH was 14.
Mixed electrolyte with different pH values is injected into an oxygen electrode chamber of the electrolyte membrane structure battery module 1 through the hydrogen peroxide circulating storage module 6; an external power source was turned on by the power switching module 2 to control the electrolyte membrane structured cell module 1, a charging voltage was applied to the electrolyte membrane structured cell module 1 in a voltage range of 0.7V to 1V, and a charging voltage-current density curve was recorded with an electrochemical workstation (energy lab XM), as shown in fig. 7 (a).
As shown in fig. 7(a), the charging current in the acid electrolyte is maximized when the system is operated in the charging mode; at pH 0.3 and charging voltage 1.0V, the charging current density was 280mA/cm2。
Example 3
The reversible battery system based on electrochemical cycle of hydrogen peroxide provided by the embodiment of the invention is basically the same as the reversible battery system of the embodiment 1, and the difference is that when the reversible battery system works in a charging mode, the reaction rate of the oxygen electrode chamber for electrolyzing hydrogen peroxide to generate oxygen is influenced by the concentration of the hydrogen peroxide. In order to study the battery performance of the system in the charging mode under different hydrogen peroxide concentrations, embodiment 3 of the present invention separately tests the charging performance of the system under different hydrogen peroxide concentrations, and the specific comparison conditions are as follows:
(1) one group of: the electrolyte is a mixed solution of sulfuric acid and hydrogen peroxide, wherein the concentration of the sulfuric acid is 0.5mol/L, and the concentration of the hydrogen peroxide is 0.25 mol/L. (2) Two groups are as follows: the electrolyte is a mixed solution of sulfuric acid and hydrogen peroxide, wherein the concentration of the sulfuric acid is 0.50mol/L, and the concentration of the hydrogen peroxide is 0.50 mol/L. (3) Three groups: the electrolyte is a mixed solution of sulfuric acid and hydrogen peroxide, wherein the concentration of the sulfuric acid is 0.50mol/L, and the concentration of the hydrogen peroxide is 1.00 mol/L. (4) Four groups: the electrolyte is a mixed solution of sulfuric acid and hydrogen peroxide, wherein the concentration of the sulfuric acid is 0.50mol/L, and the concentration of the hydrogen peroxide is 2.00 mol/L. (5) Five groups are as follows: the electrolyte is a mixed solution of sulfuric acid and hydrogen peroxide, wherein the concentration of the sulfuric acid is 0.50mol/L, and the concentration of the hydrogen peroxide is 4.00 mol/L.
Injecting 0.50mol/L sulfuric acid and hydrogen peroxide mixed electrolyte with different concentrations into an oxygen electrode chamber of the electrolyte membrane structure battery module 1 through the hydrogen peroxide circulating storage module 6; an external power source was turned on by the power switching module 2 to control the electrolyte membrane structured cell module 1, a charging voltage was applied to the electrolyte membrane structured cell module 1 in a voltage range of 0.7V to 1V, and a charging voltage-current density curve was recorded with an electrochemical workstation (energy lab XM), as shown in fig. 7 (b).
As shown in fig. 7(b), when the system is operated in the charging mode, the charging current of the system gradually increases as the concentration of hydrogen peroxide gradually increases; when the hydrogen peroxide concentration is 4.00mol/L and the charging voltage is 1.0V, the charging current density is 370mA/cm2。
Example 4
The reversible battery system based on hydrogen peroxide electrochemical cycle provided by the embodiment of the invention is basically the same as the reversible battery system of the embodiment 1, and the difference is that when the reversible battery system works in a discharge mode, an oxygen electrode chamber generates an oxygen electrochemical reduction reaction to generate hydrogen peroxide, a hydrogen electrode chamber generates a hydrogen electrochemical oxidation reaction, and the reaction rates of the two reactions are influenced by the gas flow rate. In order to study the influence of different gas flow rates on the battery performance of the system in the discharge mode, embodiment 4 of the present invention tests the discharge performance of the system at different gas flow rates, specifically, the comparison conditions are as follows:
(1) one group of: the flow rates of hydrogen and air were both 0.05L/min, and the cell operating temperature was 25 ℃.
(2) Two groups are as follows: the flow rates of hydrogen and air were both 0.10L/min, and the cell operating temperature was 25 ℃.
(3) Three groups: the flow rates of hydrogen and air were both 0.20L/min, and the cell operating temperature was 25 ℃.
(4) Four groups: the flow rates of hydrogen and air were both 0.50L/min, and the cell operating temperature was 25 ℃.
(5) Five groups are as follows: the flow rates of hydrogen and air were both 1.00L/min, and the cell operating temperature was 25 ℃.
The hydrogen of the hydrogen circulation storage module 3 is introduced into the hydrogen electrode chamber of the electrolyte membrane structure battery module 1 at different flow rates, the air of the oxygen circulation storage module 12 is introduced into the oxygen electrode chamber of the electrolyte membrane structure battery module 1 at different flow rates, and the working temperature of the battery is 25 ℃. An external electric device was connected to the electrolyte membrane structured cell module 1 through the power conversion module 2, and a discharge voltage-current density curve was recorded with the fuel cell workstation (850e), as shown in fig. 7 (c).
As shown in fig. 7(c), the discharge capacity of the electrolyte membrane structure cell when the system is operated in the discharge mode is related to the flow rate of air introduced into the oxygen electrode chamber and the flow rate of hydrogen introduced into the hydrogen electrode chamber. As the gas flow rate increases, the discharge current of the system gradually increases. When the gas flow rate is more than 0.50L/min, the discharge current does not obviously change along with the increase of the gas flow rate, and the discharge current of the system reaches a stable value of 450mA/cm2。
Example 5
The reversible battery system based on hydrogen peroxide electrochemical cycle provided by the embodiment of the invention is basically the same as the reversible battery system of the embodiment 1, and the difference is that when the reversible battery system works in a discharge mode, the working temperature of the electrolyte membrane structure battery influences the discharge capacity of the system. In order to study the influence of the working temperature of the electrolyte membrane structure battery on the battery performance of the system in the discharge mode, embodiment 5 of the present invention tests the discharge performance of the system at different working temperatures, and the specific comparison conditions are as follows:
(1) one group of: the flow rates of hydrogen and oxygen were 0.50L/min, and the cell operating temperature was 25 ℃.
(2) Two groups are as follows: the flow rates of hydrogen and oxygen were 0.50L/min, and the cell operating temperature was 40 ℃.
(3) Three groups: the flow rates of hydrogen and oxygen were 0.50L/min, and the cell operating temperature was 60 ℃.
(4) Four groups: the flow rates of hydrogen and oxygen were 0.50L/min, and the cell operating temperature was 80 ℃.
The hydrogen of the hydrogen circulation storage module 3 is led into the hydrogen electrode chamber of the electrolyte membrane structure battery module 1 at the flow rate of 0.50L/min, and the oxygen of the oxygen circulation storage module 12 is led into the oxygen electrode chamber of the electrolyte membrane structure battery module 1 at the flow rate of 0.5L/min, so that the working temperature of the battery is changed. An external electric device was connected to the electrolyte membrane structured cell module 1 via the power conversion module 2, and a discharge voltage-current density curve was recorded with a fuel cell workstation (Scribner 850e), as shown in fig. 7 (d).
Fig. 7(d) shows that when the system is operated in the discharge mode, the operating temperature affects the discharge capability of the system. The discharge current of the system is gradually increased along with the rise of the temperature, and the maximum discharge current of 900mA/cm can be output at the high temperature of 80 DEG C2。
Example 6
The reversible battery system based on hydrogen peroxide electrochemical cycle provided by the embodiment of the invention is basically the same as the reversible battery system of the embodiment 1, and the difference is that the oxygen electrode catalyst material is an oxygen electrode catalyst of a metal alloy class. To study the applicability of oxygen electrode catalysts of different types of metal alloy materials in the reversible battery system of the present invention, example 6 is performed by comparing the current densities of different catalyst materials when operating in the charging mode and the discharging mode, wherein the preparation method of the oxygen electrode catalyst of the metal alloy type comprises: 2000mg of polyvinylpyrrolidone (PVP) was weighed into 60mL of a mixed solution of ethanol-DMF-pyrrole, and a metal salt solution of a certain mass was added to obtain a mixed solution, which was reacted at 120 ℃ for 90 minutes. Separating the black precipitate at the lower layer by high speed centrifugation. The specific comparison conditions were as follows:
(1) one group is platinum amalgam. In the preparation of a platinum amalgam, the metal salt solution is prepared from 168.4mg PtCl4And 927.9mg HgI2And (4) forming. (2) Two groups adopt palladium amalgam. In the preparation method of the palladium amalgam, the metal salt solution is prepared from 88.6mg of PdCl2And 927.9mg HgI2And (4) forming. (3) Three groups are made of gold-palladium alloy. In the preparation method of the gold-palladium alloy, the metal salt solution is prepared from 151.6mg AuCl3And 177.2mg of PdCl2And (4) forming. (4) Four groups are made of copper amalgam. In the preparation method of the copper amalgam, the metal salt solution is prepared from 134.5mg CuCl2And 618.6mg HgI2And (4) forming. (5) The five groups are silver-mercury alloy. In the preparation method of the silver-mercury alloy, the metal salt solution is prepared by 143.3mg AgCl and 618.6mg HgI2And (4) forming. (6) Six groups adopt platinum-palladium amalgam. In the preparation of a platinum-palladium amalgam, the metal salt solution is prepared from 168.4mg of PtCl4、177.3mg PdCl2And 618.6mg HgI2And (4) forming.
In order to illustrate the charge and discharge capacity of the oxygen electrode catalyst material in the reversible cell system based on the electrochemical cycle of hydrogen peroxide according to the embodiment of the present invention, the catalyst materials were respectively connected to the reversible cell system according to the connection scheme of fig. 1, and a charge and discharge mode cycle test was performed, and the discharge voltage and current density data were recorded by the fuel cell workstation (Scribner 850e), the charge voltage and current density data were recorded by the electrochemical workstation (energy lab XM), and the results of comparing the performance of the oxygen electrode catalyst materials are shown in table 1.
TABLE 1 comparison of oxygen electrode catalyst Material Performance
By comparison, under the same charging voltage (0.8V) in the charging mode, the current density is in the order of platinum-palladium amalgam catalyst > platinum-amalgam catalyst > palladium-amalgam catalyst > gold-palladium alloy catalyst > copper-amalgam catalyst > silver-mercury alloy catalyst from large to small. Under the discharge mode, under the same discharge voltage (0.6V), the corresponding discharge current densities are from large to small, namely platinum-palladium amalgam catalyst, platinum-amalgam catalyst, palladium-amalgam catalyst, gold-palladium alloy catalyst, copper-amalgam catalyst and silver-mercury alloy catalyst.
Example 7
The reversible battery system based on hydrogen peroxide electrochemical cycle provided by the embodiment of the invention is basically the same as the reversible battery system of the embodiment 1, and the difference is that the oxygen electrode catalyst material is a metal nitrogen co-doped carbon material. In order to study the applicability of oxygen electrode catalysts of different types of metal nitrogen co-doped carbon materials in the reversible battery system, example 7 is to compare the current densities of different catalyst materials when the catalyst materials work in a charging mode and a discharging mode, wherein the preparation method of the metal nitrogen co-doped carbon material comprises the following steps: 1ml of aniline (purity > 98%), 0.2g of commercial activated carbon and a certain mass of metal salt were uniformly mixed into a 1N hydrochloric acid solution, and the slurry after concentration of the solution was subjected to high-temperature heat treatment at 900 ℃ for 1 hour in a nitrogen atmosphere to obtain an initial sample. And soaking the initial sample in concentrated hydrochloric acid for 24 hours, and then performing high-temperature heat treatment at 900 ℃ for 3 hours in a nitrogen atmosphere to obtain the product. The specific comparison conditions were as follows:
(1) one group selects platinum nitrogen co-doped carbon materials. In the preparation method of the platinum-nitrogen co-doped carbon material, 336.8mg of metal salt platinum chloride is added. (2) And the two groups adopt palladium-nitrogen co-doped carbon materials. In the preparation method of the palladium-nitrogen co-doped carbon material, 177.3mg of metal salt palladium chloride is added. (3) And the three groups are made of iron-nitrogen co-doped carbon materials. In the preparation method of the iron-nitrogen co-doped carbon material, the mass of the added metal salt anhydrous ferric chloride is 162.0 mg. (4) The four groups adopt manganese nitrogen co-doped carbon materials. In the preparation method of the manganese-nitrogen co-doped carbon material, the mass of the added metal salt anhydrous manganese chloride is 125.9 mg. (5) And five groups adopt copper and nitrogen co-doped carbon materials. In the preparation method of the copper-nitrogen co-doped carbon material, the mass of the added metal salt anhydrous copper chloride is 134.5 mg. (6) And six groups of the carbon materials are iron-manganese-nitrogen co-doped. In the preparation method of the iron-manganese-nitrogen co-doped carbon material, the added metal salt consists of 162.0mg of anhydrous ferric chloride and 125.9mg of anhydrous manganese chloride. (7) And the seven groups adopt iron-cobalt nitrogen co-doped carbon materials. In the preparation method of the iron-cobalt nitrogen co-doped carbon material, the added metal salt consists of 162.0mg of anhydrous ferric chloride and 165.8mg of cobalt chloride dihydrate.
In order to illustrate the charge and discharge capacity of the oxygen electrode catalyst material in the reversible cell system based on the hydrogen peroxide electrochemical cycle according to the present invention, the catalyst materials were introduced into the reversible cell system in a connection manner as shown in fig. 1, and a charge and discharge mode cycle test was performed, and the discharge voltage and current density data were recorded using a fuel cell workstation (850e), and the charge voltage and current density data were recorded using an electrochemical workstation (energy lab XM), and the results of comparing the performance of the oxygen electrode catalyst materials are shown in table 2.
TABLE 2 comparison of oxygen electrode catalyst Material Performance
Example 8
The reversible battery system based on hydrogen peroxide electrochemical cycle provided by the embodiment of the invention is basically the same as the reversible battery system of the embodiment 1, and the difference is that the oxygen electrode catalyst material is an organic metal complex. To investigate the applicability of oxygen electrode catalysts of different types of organometallic complexes in the reversible battery system of the present invention, example 8 was performed to compare the current densities of different metal complex materials when operated in the charge mode and the discharge mode, wherein the organometallic complexes were prepared by: under the protection of nitrogen, organic ligand and metal salt with certain mass are mixed and added into 25mL solvent and refluxed for 1 hour,after the reaction, the reaction mixture was cooled to room temperature, distilled water was added thereto, and methylene Chloride (CH) was added2Cl2) Extracting for 3 times, and collecting the product. Drying the collected organic phase with anhydrous sodium sulfate, and removing the solvent by rotary evaporation to obtain the final product. The specific comparison conditions were as follows:
(1) one group is porphyrin-cobalt. Porphyrin-cobalt was prepared by adding 15.3g of commercial porphyrin (Michalin) and 6.5g of anhydrous cobalt chloride to 25mL of N, N-Dimethylformamide (DMF). (2) Two groups adopt bipyridine-cobalt. In the preparation of bipyridine-cobalt, 1.5g of commercial 2, 2' -bipyridine (gukao group) and 6.5g of anhydrous cobalt chloride were added to 25mL of ethanol. (3) Three groups are selected from pyrrole-cobalt. Pyrrole-cobalt was prepared by adding 0.67g commercial pyrrole (gugguan group) and 6.5g anhydrous cobalt chloride to 25mL DMF. (4) Four groups are selected from 2, 2' -dipyridyl amine-cobalt. 2,2 '-dipyridylamine-cobalt preparation method, 1.7g of commercial 2, 2' -dipyridylamine (sigma) and 6.5g of anhydrous cobalt chloride were added to 25mL of chloroform.
In order to illustrate the charge and discharge capacity of the oxygen electrode catalyst material in the reversible cell system based on hydrogen peroxide electrochemical cycle according to the present invention, a series of cell devices having an electrolyte membrane structure were prepared by using the above catalyst materials according to the method of example 1, respectively, and a charge and discharge mode cycle test was performed in the reversible cell system based on hydrogen peroxide electrochemical cycle, and the discharge voltage and current density data were recorded using a fuel cell workstation (850e), the charge voltage and current density data were recorded using an electrochemical workstation (energy lab XM), and the results of comparing the performance of the oxygen electrode catalyst materials are shown in table 3.
TABLE 3 comparison of oxygen electrode catalyst Material Performance
Example 9
The reversible battery system based on hydrogen peroxide electrochemical cycle provided by the embodiment of the invention is basically the same as the reversible battery system of the embodiment 1, and the difference is that the oxygen electrode catalyst material is a metal ion doped polymer. To study the applicability of oxygen electrode catalysts of different types of metal ion doped polymers in the reversible battery system of the present invention, example 9 is to compare the current densities of different organic complex materials when operating in a charging mode and a discharging mode, wherein the preparation method of the metal ion doped polymer comprises: under the protection of nitrogen, 10mmol of commercial polymer material and 250mL of dilute hydrochloric acid with a certain mass of metal salt are stirred for 24 hours, the mixed solution is concentrated at 80 ℃, and the obtained mixture is filtered and dried in vacuum, thus obtaining the polymer. The specific comparison conditions were as follows:
(1) one group selects iron-doped polypyrrole materials. In the preparation of iron-doped polypyrrole, 10mmol of commercial polypyrrole (Mecanum Shanghai) and 8.11g of anhydrous ferric chloride were added to 250mL of dilute hydrochloric acid. (2) Two groups are iron-doped polypyridine materials. In the preparation of iron-doped polypyridine material, 10mmol of commercial polypyridine (Mecanum Shanghai) and 8.11g of anhydrous ferric chloride were added to 250mL of dilute hydrochloric acid. (3) And the third group is iron-doped polyaniline material. In the preparation method of the iron-doped polyaniline material, 10mmol of commercial polyaniline (Shanghai Mecline) and 8.11g of anhydrous ferric chloride are added into 250mL of diluted hydrochloric acid and stirred for 24 hours.
In order to illustrate the charge and discharge capacity of the oxygen electrode catalyst material in the reversible cell system based on hydrogen peroxide electrochemical cycle according to the present invention, a series of cell devices having an electrolyte membrane structure were prepared by using the above catalyst materials according to the method of example 1, respectively, and a charge and discharge mode cycle test was performed in the reversible cell system based on hydrogen peroxide electrochemical cycle, and the discharge voltage and current density data were recorded using a fuel cell workstation (850e), the charge voltage and current density data were recorded using an electrochemical workstation (energy lab XM), and the results of comparing the performance of the oxygen electrode catalyst material were shown in table 4.
TABLE 4 comparison of oxygen electrode catalyst Material Performance
Comparative example 1
The conventional reversible fuel cell device includes the following parts: the oxygen electrode catalyst adopts a commercial 46.7 percent Pt/C catalyst, and the hydrogen electrode catalyst adopts a commercial 20 percent Pt/C catalyst; the oxygen electrode gas diffusion layer is a titanium mesh, the oxygen electrode runner plate is a titanium metal runner plate, and the oxygen electrode collector plate is a gold-plated titanium plate; the hydrogen electrode gas diffusion layer is carbon paper, the hydrogen electrode runner plate is a graphite runner plate, the collector plate is a gold-plated copper plate, the diaphragm is a commercial proton exchange membrane Nafion N-211, and the sealing ring is a fiber reinforced polytetrafluoroethylene membrane.
Comparative example 2
The conventional reversible fuel cell device includes the following parts: the oxygen electrode catalyst adopts a commercial 20% Ir/C catalyst, and the hydrogen electrode catalyst adopts a commercial 20% Pt/C catalyst; the oxygen electrode gas diffusion layer is a titanium mesh, the oxygen electrode runner plate is a titanium metal runner plate, and the oxygen electrode collector plate is a gold-plated titanium plate; the hydrogen electrode gas diffusion layer is carbon paper, the hydrogen electrode runner plate is a graphite runner plate, the collector plate is a gold-plated copper plate, the diaphragm is a commercial proton exchange membrane Nafion N-211, and the sealing ring is a fiber reinforced polytetrafluoroethylene membrane.
The charge and discharge performance of the reversible fuel cell system of example 1 of the present invention was compared with that of the conventional reversible fuel cell devices (comparative example 1 and comparative example 2), and the result is shown in fig. 8. The traditional reversible fuel cell device is adopted to carry out the cyclic charge and discharge performance test, and the specific operation is as follows:
in the charging mode, water was injected into the oxygen electrode chamber of a conventional reversible fuel cell, and a voltage was applied between the hydrogen electrode and the oxygen electrode thereof in a range of 1.2V to 2.0V, and charging voltage-current density data was recorded with an electrochemical workstation (energy lab XM). And collecting oxygen and hydrogen generated by the oxygen electrode and the hydrogen electrode chamber respectively. In the discharge mode, oxygen is introduced into the oxygen electrode chamber of the conventional reversible fuel cell, hydrogen is introduced into the hydrogen electrode chamber, the hydrogen electrode and the oxygen electrode are connected to an external electronic load, and the discharge voltage and current are recorded by a fuel cell workstation (850 e). The oxygen electrode chamber generates a four-electron oxygen reduction reaction to generate water, and the hydrogen electrode chamber generates an electrochemical hydrogen oxidation reaction; the current increases with decreasing discharge voltage. The generated water does not need to be collected and stored.
As shown by the results of fig. 8, the conventional reversible fuel cells of comparative examples 1 and 2 required an initial charging voltage of 1.5V in the charging mode, which was higher than the theoretically required 1.23V, corresponding to a charging voltage efficiency of only 80% at 1.5V. The reversible battery system in embodiment 1 of the present invention can start to work at an initial charging voltage of 0.7V, which is close to a theoretical charging voltage of 0.7V, and the corresponding charging voltage efficiency is close to 100%. The initial discharge voltage of the conventional reversible fuel cells of comparative examples 1 and 2, when operated in discharge mode, was at most 1V, lower than the theoretical discharge voltage of 1.23V, corresponding to a discharge voltage efficiency of 81%; the reversible battery system of embodiment 1 of the present invention can start discharging at an initial discharge voltage of 0.7V, which is close to the theoretical maximum discharge voltage of 0.7V, and has a voltage efficiency close to 100%.
Based on the data in fig. 8, we compared the charging voltage efficiency, the discharging voltage efficiency, and the charging and discharging cycle energy efficiency of the reversible fuel cell system based on the electrochemical cycle of hydrogen peroxide according to example 1 of the present invention with those of the conventional reversible fuel cells of comparative example 1 and comparative example 2 at different charging/discharging current densities, as shown in table 5.
Table 5 results of comparing the performance of the reversible cell systems of example 1 and comparative examples 1-2
The calculation formula of the voltage efficiency and the energy conversion efficiency is as follows:
as is evident from comparison of the data in table 5, the charge/discharge voltage efficiency and the charge/discharge cycle energy efficiency of the reversible cell system of example 1 of the present invention are higher than those of the conventional reversible fuel cell at the same charge/discharge current density.
Comparative example 3
Comparative example 3 provides a reversible battery system based on hydrogen peroxide electrochemical cycle substantially the same as the reversible battery system of example 1, except that a commercial Pt/C catalyst was used as an oxygen electrode catalyst in place of the oxygen electrode catalyst in the reversible battery system based on hydrogen peroxide electrochemical cycle of example 1. The method specifically comprises the following steps: the oxygen electrode catalyst adopts a commercial 46.7 percent Pt/C catalyst, and the hydrogen electrode catalyst adopts a commercial 20 percent Pt/C catalyst; the oxygen electrode gas diffusion layer is a graphite plate, the oxygen electrode runner plate is a graphite runner plate, and the oxygen electrode collector plate is a gold-plated copper plate; the hydrogen electrode gas diffusion layer is carbon paper, the hydrogen electrode runner plate is a graphite runner plate, the collector plate is a gold-plated copper plate, the diaphragm is a commercial proton exchange membrane Nafion N-211, and the sealing ring is a fiber reinforced polytetrafluoroethylene membrane.
The results of comparing the charge and discharge performance of the reversible battery system of example 1 of the present invention with that of the reversible battery system of comparative example 3 are shown in fig. 9. The device is used for testing the cyclic charge and discharge performance, and the specific operation is as follows:
in the charging mode, a mixed electrolyte of hydrogen peroxide and sulfuric acid was injected into the oxygen electrode chamber of the reversible fuel cell, and a voltage was applied between the hydrogen electrode and the oxygen electrode thereof in a range of 0.7V to 1.0V, and charging voltage-current density data was recorded using an electrochemical workstation (energy lab XM). And collecting oxygen and hydrogen generated by the oxygen electrode chamber and the hydrogen electrode chamber respectively. In the discharge mode, oxygen is introduced into the oxygen electrode chamber of the reversible fuel cell, hydrogen is introduced into the hydrogen electrode chamber, the hydrogen electrode and the oxygen electrode are connected with an external electronic load, and a fuel cell workstation (850e) is used for recording discharge voltage-current density data. And (4) carrying out titration analysis on the solution after gas-liquid separation by using a potassium permanganate solution, and determining the components of the oxygen electrode chamber product.
As shown in fig. 9, the reversible cell system of comparative example 3 operated in the charge mode, the initial operating voltage was close to 0.7V. The commercial Pt/C catalyst can catalyze the electrochemical oxidation reaction of hydrogen peroxide in the oxygen electrode chamber to generate oxygen, and generate hydrogen in the hydrogen electrode chamber. However, when the discharge mode is operated, the initial operating voltage is 0.9V, which is higher than the theoretical potential (0.7V) for generating hydrogen peroxide. This indicates that during operation in the discharge mode, the commercial Pt/C catalyst catalyzes the four-electron oxygen reduction reaction in the oxygen electrode chamber to produce water, and the electrochemical hydrogen oxidation reaction occurs in the hydrogen electrode chamber. And (3) titrating the product of the oxygen electrode chamber by using a potassium permanganate solution, and confirming that the product of the oxygen electrode chamber is water without color change reaction. Commercial Pt/C catalysts are unable to complete the hydrogen peroxide electrochemical cycling process.
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions and improvements made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A reversible battery system based on hydrogen peroxide electrochemical cycling, comprising: the hydrogen storage system comprises an electrolyte membrane structure battery module, a hydrogen circulating storage module, an oxygen circulating storage module, a hydrogen peroxide circulating storage module and a power supply conversion module;
the electrolyte membrane structure cell module includes:
the hydrogen electrode chamber is provided with a hydrogen gas inlet and a hydrogen gas outlet; the hydrogen circulation storage module is respectively communicated with the hydrogen inlet and the hydrogen outlet; a hydrogen electrode and a hydrogen electrode catalyst layer are arranged in the hydrogen electrode chamber;
the oxygen electrode chamber is provided with an oxygen electrode chamber inlet and an oxygen electrode chamber outlet; the oxygen electrode chamber inlet is respectively communicated with the oxygen circulating storage module and the hydrogen peroxide circulating storage module; an oxygen electrode gas-liquid separation module is connected to an outlet of the oxygen electrode chamber and is respectively communicated with the oxygen circulating storage module and the hydrogen peroxide circulating storage module; the oxygen electrode chamber is internally provided with an oxygen electrode and an oxygen electrode catalyst layer;
the electrolyte membrane is arranged between the hydrogen electrode chamber and the oxygen electrode chamber and is used for separating the oxygen electrode chamber from the hydrogen electrode chamber;
the power supply conversion module is respectively connected with the hydrogen electrode and the oxygen electrode, and can switch the working mode of the electrolyte membrane structure battery module into a charging mode or a discharging mode;
when the working mode of the electrolyte membrane structure battery module is a charging mode, the oxygen electrode catalyst layer can catalyze the oxidation of hydrogen peroxide in the oxygen electrode chamber to generate oxygen;
when the working mode of the electrolyte membrane structure battery module is a discharging mode, the oxygen electrode catalyst layer can catalyze the two-electron oxygen in the oxygen electrode chamber to reduce and generate hydrogen peroxide.
2. The reversible battery system based on electrochemical cycle of hydrogen peroxide according to claim 1, wherein the electrolyte membrane is capable of blocking hydrogen peroxide within the oxygen electrode chamber; the electrolyte membrane is a composite membrane of any one or more of a proton exchange membrane, an anion exchange membrane, a hydroxyl ion exchange membrane and a solid electrolyte membrane.
3. The reversible battery system based on hydrogen peroxide electrochemical cycle of claim 1, wherein the hydrogen gas cycle storage module is used for collecting and storing hydrogen gas in a charging mode or delivering and cycling hydrogen gas in a discharging mode;
the oxygen circulation storage module is used for collecting and storing oxygen in a charging mode of the system or conveying and circulating oxygen or air in a discharging mode;
the hydrogen peroxide circulating storage module is used for conveying and circulating hydrogen peroxide electrolyte in a charging mode or collecting and storing hydrogen peroxide electrolyte in a discharging mode.
4. The reversible battery system based on hydrogen peroxide electrochemical cycle of claim 3, wherein the hydrogen peroxide cycle storage module comprises a hydrogen peroxide electrolyte storage tank and a circulation pump, and the hydrogen peroxide electrolyte storage tank is communicated with the oxygen electrode chamber inlet through the circulation pump.
5. The reversible battery system based on hydrogen peroxide electrochemical cycle as claimed in claim 1, wherein the oxygen electrode gas-liquid separation module comprises a gas-liquid separation device for performing gas-liquid separation on the hydrogen peroxide electrolyte and the oxygen output from the oxygen electrode chamber outlet, storing the separated hydrogen peroxide electrolyte in the hydrogen peroxide cycle storage module, and storing the separated oxygen in the oxygen cycle storage module.
6. The reversible battery system based on hydrogen peroxide electrochemical cycle of claim 1, wherein the hydrogen electrode catalyst layer is composed of Pt/C catalyst, binder and gas diffusion layer;
the oxygen electrode catalyst layer is composed of an oxygen electrode catalyst material, a binder and a gas diffusion layer;
the oxygen electrode catalyst material is platinum amalgam, palladium amalgam, gold palladium alloy, copper amalgam, silver amalgam, platinum-nitrogen co-doped carbon material, palladium-nitrogen co-doped carbon material, cobalt-nitrogen co-doped carbon material, iron-nitrogen co-doped carbon material, manganese-nitrogen co-doped carbon material, copper-nitrogen doped carbon material, iron-manganese-nitrogen co-doped carbon material, iron-cobalt-nitrogen co-doped carbon material, porphyrin metalloid complex, bipyridine metal complex, polypyridine multidentate chelate metalloid complex, bipyridine metalloid complex, polypyrrole chelate metalloid complex, 2' -bipyridine amine metal complex, iron-doped polypyrrole, cobalt-doped polypyrrole, manganese-doped polypyrrole, copper-doped polypyrrole, platinum-doped polypyrrole, palladium-doped polypyrrole, iron-doped polypyridine, cobalt-doped polypyridine, manganese-doped polypyridine, copper-doped polypyridine, Platinum-doped polypyridine and palladium-doped polypyridine; iron-doped polyaniline, cobalt-doped polyaniline, manganese-doped polyaniline, copper-doped polyaniline, platinum-doped polyaniline and palladium-doped polyaniline.
7. The reversible battery system based on hydrogen peroxide electrochemical cycle according to claim 6, wherein the metal complex ion in porphyrin-based metal complex, bipyridine-based metal complex, polypyridine polydentate chelating metal complex, bipyridine-based metal complex, polypyrrole chelating metal complex, 2' -bipyridine-based metal complex is Fe2+、Fe3+、Co2+、Co3+、Cu2+、Mn2+、Pt2+、Pd2+Any one of them.
8. A method of charging and discharging a reversible battery system based on hydrogen peroxide electrochemical cycle according to claim 1, when the reversible battery system is operated in a charging mode, the method comprising:
s101, introducing a hydrogen peroxide electrolyte in the hydrogen peroxide circulating storage module into the oxygen electrode chamber;
s102, the hydrogen peroxide circulating storage module is communicated with an external power supply through the power supply conversion module, the external power supply applies voltage between the oxygen electrode and the hydrogen electrode, so that hydrogen peroxide in the oxygen electrode chamber is converted into oxygen under the action of the oxygen electrode catalyst layer, and the hydrogen electrode chamber generates electrochemical hydrogen evolution reaction to generate hydrogen;
s103, collecting and storing the hydrogen generated in the hydrogen electrode chamber in the hydrogen circulation storage module, and separating and collecting the oxygen generated in the oxygen electrode chamber in the oxygen circulation storage module.
Or when the reversible battery system is operated in a discharge mode, the method is as follows:
s201, the hydrogen peroxide circulating storage module is communicated with external power equipment or power storage equipment through a power conversion module; then introducing the hydrogen in the hydrogen circulation storage module into the hydrogen electrode chamber, and introducing the oxygen or air in the oxygen circulation storage module into the oxygen electrode chamber;
s202, hydrogen electrochemical oxidation reaction occurs in the hydrogen electrode chamber, two-electron oxygen reduction reaction occurs in the oxygen electrode chamber to generate hydrogen peroxide, and voltage and current are output;
s203, the oxygen electrode gas-liquid separation module separates and collects the oxygen and the hydrogen peroxide solution output by the oxygen electrode chamber.
9. The charging and discharging method of a reversible battery system based on hydrogen peroxide electrochemical cycle as claimed in claim 8, wherein in S101, the flow rate of the hydrogen peroxide electrolyte into the oxygen electrode chamber is 10-300 mL/min; the concentration of the hydrogen peroxide electrolyte is 0.1-90 wt%; the pH value of the hydrogen peroxide electrolyte is-3-17;
in S102, in a charging mode, the electrolysis temperature of the electrolyte membrane structure battery module is 10-80 ℃; the voltage applied between the oxygen electrode and the hydrogen electrode by the external power supply is 0.7V-1V.
10. The charge-discharge method of a reversible battery system based on hydrogen peroxide electrochemical cycle as claimed in claim 8, wherein in S201, the flow rate of hydrogen, oxygen or air is 0.05L/min to 1.00L/min;
in S202, in a discharging mode, the reaction temperature of the electrolyte membrane structure battery module is 10-80 ℃, and the discharging voltage is 0-0.8V;
in S203, the concentration of the hydrogen peroxide solution is 0.1-90 wt%.
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