CN114464932B - Method for improving performance of metal-air battery by using high voltage - Google Patents
Method for improving performance of metal-air battery by using high voltage Download PDFInfo
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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
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a method for improving the performance of a metal-air battery by utilizing high voltage, which comprises the following steps: the metal-air battery is placed in a high-pressure container, oxygen-containing gas is filled into the high-pressure container until the pressure in the high-pressure container is 15-2000 atm, and then constant pressure is maintained and the battery is kept stand for 2-6 hours. The method of the invention can improve the capacity of the metal-air battery, can obviously improve the multiplying power performance and stability of the battery, and meets the practical requirements for high-power batteries.
Description
Technical Field
The invention relates to a method for improving the performance of a metal-air battery by utilizing high voltage, belonging to the technical field of new energy.
Background
The need for new clean energy sources with high energy density is now becoming urgent due to the limited reserves of fossil fuels and the problems of greenhouse effect and environmental pollution caused by the massive burning of fossil fuels. Among them, fuel cells and secondary batteries are hot spots of interest. Among the fuel cells, the hydrogen fuel cell has advantages of sufficient reactant reserves and high energy density, but the reactant is produced at high cost and is inflammable and explosive, so that mass production and use of the hydrogen fuel cell are greatly limited. Lithium ion batteries are the most widely used secondary batteries at present, and have the advantages of high stability, rechargeable use and the like, but the low energy density of the batteries limits the application of the batteries as power batteries on large-scale equipment. Therefore, developing a secondary battery having a large capacity, high stability and excellent rate performance has a very important practical application value.
Metal-air batteries are very promising candidates for high power batteries because of their high specific energy density. The current common metal-air battery uses alkali metal, alkaline earth metal and partial transition metal as a negative electrode, uses pure oxygen or oxygen in air as a positive electrode active substance, and the common metal-air battery comprises a lithium-oxygen battery, a magnesium-air battery, a zinc-air battery, an aluminum-air battery and the like. Unlike conventional lithium ion batteries, metal-air batteries employ an open structure so that air or oxygen can reach the positive electrode to participate in the reaction. Therefore, there is no upper limit to the capacity of the positive electrode in theory, and the energy density of the metal-air battery is also made much higher than that of other secondary batteries. However, due to limitations of the charge-discharge mechanism, the high rate performance of metal-air batteries is generally poor, and the cycle life is significantly shorter than that of conventional lithium ion batteries. As a high-power battery, in addition to having as high an energy density as possible, excellent rate performance and as long a cycle life as possible are two other necessary conditions. Because of this, current metal-air batteries have not yet met practical requirements.
In order to solve these problems, researchers have tried various methods including loading a catalyst on a positive electrode sheet, developing a suitable electrolyte, adding a redox initiator, a corrosion inhibitor to the electrolyte, taking protective measures for a corrosion-susceptible metal negative electrode, and the like. These methods do effectively improve the rate performance and extend the life of the battery, but also increase the difficulty and cost of the battery preparation, reduce the specific capacity, and limit the large-scale commercial application of the battery. Furthermore, since the metal-air battery is an open structure, the toxicity of the added components also affects the safety of use.
Therefore, there is a need to develop a new method for improving the performance of a metal-air battery with low cost and high safety, and to realize the stable discharge of the metal-air battery with high multiplying power and long service life, so that the metal-air battery meets the requirement of being used as a high-power battery. For this purpose, the present invention is proposed.
Disclosure of Invention
In view of the shortcomings of the prior art, the invention provides a method for improving the performance of a metal-air battery by utilizing high voltage. The method can effectively improve the solubility of oxygen in the electrolyte, thereby breaking through the bottleneck of low solubility and slow transportation of oxygen in the electrolyte and realizing the high-rate and long-service-life stable discharge of the metal-air battery; in addition, the method does not need noble metal and toxic chemical reagent, and the battery has low manufacturing cost and higher safety, and is particularly suitable for large-scale production and application.
Description of the terminology:
atmospheric pressure: one atmosphere in the present invention means 0.1MPa.
The technical scheme of the invention is as follows:
a method for improving the performance of a metal-air battery using high voltage comprising the steps of:
the metal-air battery is placed in a high-pressure container, oxygen-containing gas is filled into the high-pressure container until the pressure in the high-pressure container is 15-2000 atm, and then constant pressure is maintained and the battery is kept stand for 2-6 hours.
According to the present invention, preferably, the metal-air battery is a lithium-oxygen battery, a magnesium-air battery, a magnesium-oxygen battery, an aluminum-air battery, an aluminum-oxygen battery, a zinc-air battery, or a zinc-oxygen battery.
According to the present invention, preferably, the oxygen-containing gas is oxygen, an oxygen-nitrogen mixed gas, an oxygen-argon mixed gas, an oxygen-neon mixed gas or compressed air; more preferably oxygen or an oxygen-argon mixture.
According to the present invention, the oxygen-containing gas preferably has an oxygen content of 1 to 100% by volume, more preferably 20 to 100% by volume, and still more preferably 60 to 100% by volume.
According to the present invention, the pressure of the oxygen-containing gas filled into the high pressure vessel is preferably 20 to 1000 atmospheres, more preferably 30 to 600 atmospheres, still more preferably 30 to 300 atmospheres.
According to the present invention, the partial pressure of oxygen is preferably 10 to 200 atmospheres, more preferably 40 to 100 atmospheres, when the high pressure vessel is filled with an oxygen-containing gas.
According to the present invention, it is preferable that the constant pressure is maintained for a period of 2.5 hours.
According to the invention, the preparation method of the metal-air battery is the prior art; preferably, the metal-air battery is prepared according to the following method:
(1) Preparation of positive plate
The preparation is carried out by one of the following methods:
adding the active component and the binder into the solvent according to the mass ratio of 2:1-9:1, wherein the mass ratio of the active component to the volume of the solvent is 20-200mg:1mL, uniformly stirring to obtain a mixture, coating the mixture on a current collector, and the coating amount of the active component is 0.1-10mg/cm 2 Vacuum drying for later use; or (b)
Ii, directly vacuum drying the integrated electrode to prepare an electrode sheet for later use; or (b)
Adding the active component, the binder slurry and the conductive carbon black into a solvent according to the mass ratio of 1-4.5:1-4.5:1, wherein the mass ratio of the active component to the solvent is 20-200mg:1mL, stirring uniformly, and pressing into a sheet with the thickness of 0.2-0.3 mm; uniformly mixing the active component and the binder slurry according to the mass ratio of 1:1-1:9, and pressing into a sheet with the thickness of 0.3 mm; hot-pressing the two obtained thin sheets and a current collector together, and then drying in vacuum to obtain a positive plate with a three-layer structure; the binder slurries all had a solids content of 60wt%.
(2) Preparation of electrolyte
Adding metal salt, an additive and an oxidation-reduction initiator into a solvent, and stirring until the metal salt, the additive and the oxidation-reduction initiator are completely dissolved to obtain electrolyte with the metal salt concentration of 0.1-10.0 mol/L;
(3) Battery assembly
And (3) sequentially loading the positive electrode plate soaked by the electrolyte, the diaphragm soaked by the electrolyte and the metal negative electrode plate into a battery shell, and compacting by a press to obtain the metal-air battery.
Preferably, the active components in the step (1) are one or more than two of acetylene black, active carbon, graphene, doped graphene, graphene oxide, carbon nanotubes, conductive carbon black, noble metal and oxides thereof, transition metal oxides, rare earth metal oxides and platinum-magnesium alloy; the noble metal is ruthenium, gold, platinum or palladium; the transition metal oxide is Mn 3 O 4 Cobalt oxide,Iron oxide; the rare earth metal oxide is cerium dioxide.
Preferably, the binder in step (1) is perfluorosulfonic acid (Nafion), polyvinylidene fluoride (PVDF), or Polytetrafluoroethylene (PTFE).
Preferably, the solvent in the step (1) is one or a combination of more than two of ethanol, isopropanol, N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), N-Dimethylformamide (DMF), dimethylacetamide (DMAC) and water.
Preferably, the current collectors in the step (1) are carbon paper, carbon fiber cloth, graphene paper, nickel mesh, stainless steel mesh, copper mesh, foam nickel, noble metal porous membrane or carbon nanotube membrane; the noble metal porous membrane is a porous gold membrane, a porous silver membrane or a porous platinum membrane.
Preferably, the integrated electrode in the step (1) is an electrode of which the active component and the current collector are of the same species; preferably, the integrated electrode is one of graphene paper, ceria-modified graphene paper, graphene oxide paper, a carbon nanotube film, a noble metal porous net, a transition metal porous film and a transition metal porous net; the noble metal is gold, platinum or silver; the transition metal is nickel, titanium or iron.
Preferably, the metal salt in step (2) is LiClO 4 、LiCF 3 SO 3 、LiN(CF 3 SO 2 ) 2 、Mg(NO 3 ) 2 、NaNO 3 One or more than two of NaOH, KOH, zinc acetate, liBr, liI, naCl, naBr, zinc chloride and zinc oxide.
Preferably, the solvent in the step (2) is dimethyl sulfoxide (DMSO), N-Dimethylformamide (DMF), dimethyl ether triethylene glycol (TEGDME), tetraethylene glycol dimethyl ether, diglyme, diethylene glycol dimethyl ether (DEGDME), CH 3 CN, trihexyl (tetradecyl) phosphine chloride, water, or a combination of two or more thereof.
Preferably, the additive in step (2) is 1-methoxy-2- (1, 2-tetrafluoroethoxy) ethane (FE 1), 1, 4-diazabicyclo [2, 2)]Octane (D)ABCO), water-soluble graphene, na 2 SnO 3 、In(OH) 3 Zinc oxide, zinc chloride, cetyltrimethylammonium bromide, KNaC 4 H 4 O 6 One or a combination of two or more of them; the additive is 1-methoxy-2- (1, 2-tetrafluoroethoxy) ethane (FE 1) or 1, 4-diazabicyclo [2, 2)]Octane (DABCO), na 2 SnO 3 、In(OH) 3 Zinc oxide, zinc chloride, cetyltrimethylammonium bromide, KNaC 4 H 4 O 6 When one or more than two of the above are combined, the concentration of the additive in the electrolyte is 0-2.0mol/L; when the additive is water-soluble graphene, the mass concentration of the additive in the electrolyte is 0-5wt%.
Preferably, the oxidation-reduction initiator in the step (2) is one or more than two of tetrabutylammonium chloride, vanadyl acetylacetonate, triethyliodinated sulfur (TESI), tetrathiafulvalene (TTF), ferrocene, dimethyl phenazine (DMPZ), tris [4- (diethylamino) phenyl ] amine (TDPA), heme oxygenase, N-Methyl Phenothiazine (MPT), 2, 6-tetramethylpiperidine oxide (TEMPO); the concentration of the oxidation-reduction initiator in the electrolyte is 0-500.0mmol/L.
Preferably, the separator in the step (3) is a glass fiber film, a graphene oxide film, a porous polypropylene fiber film, or a ZrO film 2 A solid electrolyte membrane, a polyethylene oxide membrane, or a polyethylene membrane.
Preferably, the metal negative electrode sheet in the step (3) is lithium sheet or LiFePO 4 Magnesium flakes, magnesium alloys, aluminum flakes, aluminum alloys or zinc flakes; the magnesium alloy is an alloy of magnesium and one or more than two of aluminum, tin, nickel and lead; the aluminum alloy is an alloy of aluminum and one or more than two of magnesium, tin and cerium.
Preferably, in step (3), the assembly of the battery is performed in a glove box, and the protective gas in the glove box is nitrogen, argon or neon.
According to the present invention, preferably, the oxygen-containing gas is supplied from a high-pressure gas cylinder or a high-pressure gas control apparatus; the high-pressure gas control device is an existing device in the field.
The invention has the technical characteristics and beneficial effects that:
1. compared with the existing method, the method for remarkably improving the performance of the metal-air battery by utilizing high voltage has the following significant improvements: on one hand, the discharge reaction kinetic speed of the metal-air battery is greatly accelerated by improving the pressure of the gas, the multiplying power performance of the battery is remarkably improved, and the metal-air battery can be used as a high-power battery; on the other hand, the method of the invention does not use toxic materials, and the battery has lower manufacturing cost and higher use safety, thus being particularly suitable for mass production and application.
2. The method of the invention has strong universality, and can be used in combination with other methods (such as adding a catalyst and the like) to further improve the performance of the metal-air battery. The method of the invention can be widely applied to various metal-air battery systems, and the atmosphere and the pressure can be flexibly regulated and controlled according to the requirements of different application occasions.
3. By utilizing the method, the overpotential of the battery can be greatly reduced, the stability and the high-rate performance of the battery are obviously improved, and the high-current and high-stability charge-discharge of the metal-air battery in high-pressure gas is realized; meanwhile, other optimization modes can be combined, so that the battery performance is further improved, and the large-scale practical application of the metal-air battery is realized.
Drawings
Fig. 1 is a graph showing comparison of charge-discharge performance of the lithium-oxygen battery prepared in example 1 in oxygen at 1 atmosphere and 100 atmospheres.
Fig. 2 is a top 10-turn charge-discharge curve of the lithium-oxygen battery prepared in example 1 in oxygen at 1 atmosphere and 100 atmospheres.
Fig. 3 is a graph showing comparison of charge-discharge properties of the lithium-oxygen battery prepared in example 2 at various pressures.
Fig. 4 is an electrochemical C-V curve for the lithium-oxygen cell prepared in example 3 at various pressures.
Fig. 5 is initial discharge voltages of the lithium-oxygen battery prepared in example 3 at various pressures.
Fig. 6 is a charge-discharge curve of the lithium-oxygen battery prepared in example 4 in oxygen gas at 1 atmosphere and 50 atmospheres.
Detailed Description
The method of the present invention will be further described with reference to the following specific examples, but is not limited thereto.
Meanwhile, the experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials, unless otherwise specified, are commercially available.
Example 1
A method for improving the performance of a metal-air battery using high voltage comprising the steps of:
(1) Preparation of positive plate
Adding Acetylene Black (AB) and a binder polyvinylidene fluoride (PVDF) into N-methyl pyrrolidone (NMP) according to a mass ratio of 8:2, wherein the mass ratio of the Acetylene Black (AB) to the NMP is 20 mg/1 mL, fully stirring to obtain a uniformly dispersed mixture, coating the mixture on carbon paper, and the coating amount of active components is 0.3mg/cm 2 And vacuum drying, and placing into a glove box for standby.
(2) Preparation of electrolyte
LiCF is added 3 SO 3 Dissolving in dimethyl ether triethylene glycol (TEGDME), stirring to dissolve completely, and preparing into LiCF 3 SO 3 An electrolyte with a concentration of 1.0 mol/L.
(3) Battery assembly
The battery assembling process is completed in a glove box filled with high-purity argon; and (3) during assembly, the battery assembly is arranged in a battery shell according to the sequence of the positive electrode sheet soaked by the electrolyte, the glass fiber film soaked by the electrolyte and the lithium sheet, and the battery assembly is pressed by a press.
(4) High voltage treatment of batteries
In a glove box, the assembled battery is filled into a high-pressure container, and the battery is sealed after being connected with a test electrode; taking the high-pressure container out of the glove box, connecting a high-pressure gas path, and connecting a test electrode to test equipment; the high-pressure gas is provided by a high-pressure gas steel cylinder or a high-pressure gas control device.
Filling oxygen-containing gas into the high-pressure container through the high-pressure gas path until the pressure in the high-pressure container is 100 atmospheres, then maintaining constant pressure and standing for 2.5 hours to ensure that the battery reaches a stable state; the oxygen-containing gas is oxygen.
The charge-discharge performance of the lithium-oxygen battery prepared in this example was tested according to the parameters of the battery cutoff capacity of 500 milliampere hours/g and the current density of 100 milliampere/g by setting the charge-discharge program. As a comparison, the performance of the same lithium-oxygen battery described above in 1 atmosphere of oxygen was tested using the exact same charge-discharge procedure, and the results are shown in fig. 1; the first 10 cycles of the charge-discharge curve of the lithium-oxygen cell in oxygen at 1 atmosphere and 100 atmospheres is shown in fig. 2.
As can be seen from fig. 1, when the pressure of oxygen, i.e., the pressure in the high-pressure container, is increased from 1 atmosphere to 100 atmospheres, not only is the discharge voltage of the lithium-oxygen battery significantly increased, but also the charge-discharge cycle life of the battery is greatly prolonged from 31 times to 319 times, and the cycle life of the battery is prolonged by one order of magnitude. In addition, fig. 2 shows that when the pressure of oxygen is increased from 1 atmosphere to 100 atmospheres, the discharge voltage of the lithium-oxygen battery is significantly increased while its charge voltage is greatly decreased. This condition significantly reduces the overpotential of the battery and improves the stability of the battery.
Example 2
A method for improving the performance of a metal-air battery using high voltage is as described in example 1, except that: the pressure in the high pressure vessel was 6 values of 1, 10, 25, 50, 75 and 100 atmospheres, respectively.
The discharge current density is increased to 1000 milliamp/gram in the test, and the comparison chart of the charge-discharge performance of the prepared lithium-oxygen battery under different pressures is shown as figure 3, and as can be seen from figure 3, when the discharge current is increased to 1000 milliamp/gram, the cycle life of the battery in oxygen with 1 atmosphere is only 2 times, and as the oxygen pressure, namely the pressure in a high-pressure container, is continuously increased, the discharge voltage of the lithium-oxygen battery is improved, and the charge-discharge cycle life of the battery is further increased from 2 times at 1 atmosphere to 176 times at 100 atmospheres. This result shows that: the improvement of the oxygen pressure not only can improve the cycle stability of the battery, but also can greatly improve the high-current discharge (multiplying power) performance of the battery, which is an important index for a high-capacity power battery.
Example 3
A method for improving the performance of a metal-air battery using high voltage is as described in example 1, except that: the pressure in the high pressure vessel was 1, 20, 40, 60, 80 and 100 atmospheres, respectively.
The electrochemical C-V curves of the prepared lithium-oxygen battery under different pressures are shown in figure 4, the voltage scanning speed is 0.1mV/s during testing, and the voltage scanning range is 2.0-4.5V. As can be seen from fig. 4, as the pressure in the high-voltage container increases, the battery discharge current density increases significantly, and the initial discharge voltage increases. In fig. 5, a plot of the initial discharge voltage of the battery with respect to the pressure is given, and it can be seen that the initial discharge voltage of the battery gradually increases with increasing pressure, and a saturation tendency occurs around 40 atmospheres.
Example 4
A method for improving the performance of a metal-air battery using high voltage is as described in example 1, except that: the active component used in the preparation of the positive plate is noble metal Ru/RuO 2 A mixture with carbon nanotubes; the pressure in the high pressure vessel was 1 and 50 atmospheres, respectively.
The discharge current at the time of the battery performance test was 100 milliamperes/gram, the cut-off voltage was 2.0 volts, and the charge-discharge curve of the prepared lithium-oxygen battery is shown in fig. 6, and fig. 6 shows that: when the pressure of oxygen, i.e., the pressure in the high-pressure vessel, was 1 atm, the discharge capacity of the battery was 5000 milliamp-hours/gram; when the pressure of oxygen, i.e., the pressure in the high-pressure vessel, was increased to 50 atm, the discharge capacity of the battery was increased to 9000 milliamp hour/gram. Further, the discharge voltage of the battery in the oxygen gas of 50 atmospheres was increased, the charge voltage was decreased, and the overpotential of the battery was significantly reduced, as compared with the case in the oxygen gas of 1 atmosphere.
Example 5
A method for improving the performance of a metal-air battery using high voltage is as described in example 1, except that: the active component used in the preparation of the positive plate is graphene, the current collector is nickel screen, and the solvent used is N, N-Dimethylformamide (DMF); the solvent used in preparing electrolyte is dimethyl sulfoxide (DMSO); the pressure in the high pressure vessel was 15 atmospheres.
Example 6
A method for improving the performance of a metal-air battery using high voltage is as described in example 1, except that: the active component used in the preparation of the positive plate is conductive carbon black (Super P), the current collector is a stainless steel mesh, and the binder is polytetrafluoroethylene; the metal salt used to prepare the electrolyte is lithium perchlorate (LiClO) 4 ) The solvent is dimethyl sulfoxide (DMSO); the pressure in the high pressure vessel was 25 atmospheres.
Example 7
A method for improving the performance of a metal-air battery using high voltage is as described in example 1, except that: the active component and the current collector are both graphene paper; the metal salt used in preparing the electrolyte is LiN (CF) 3 SO 2 ) 2 The solvent is diglyme, and a redox initiator 2, 6-tetramethylpiperidine oxide (TEMPO) is also added, wherein the concentration of the redox initiator in the electrolyte is 10mmol/L; the pressure in the high pressure vessel was 75 atmospheres.
Example 8
A method for improving the performance of a metal-air battery using high voltage is as described in example 1, except that: the active component used in the preparation of the positive plate is conductive carbon black, the current collector is a stainless steel net, and the used binder is polytetrafluoroethylene; the metal salt used to prepare the electrolyte is LiN (CF) 3 SO 2 ) 2 The solvent is dimethyl ether triethylene glycol, and a redox initiator of tris [4- (diethylamino) phenyl ] is also added]Amine (TDPA), the concentration of the oxidation-reduction initiator in the electrolyte is 5mmol/L; the pressure in the high pressure vessel was 150 atmospheres.
Example 9
Method for improving performance of metal-air battery by using high voltage as in example1, except that: the active component used in the preparation of the positive plate is nitrogen-doped graphene, and the current collector is carbon fiber cloth; the metal salt used in preparing the electrolyte is lithium perchlorate (LiClO) 4 ) The solvent is dimethyl sulfoxide (DMSO); the oxygen-containing gas was a mixed gas of 10% oxygen and 90% argon, and the pressure in the high-pressure vessel was 200 atm.
Example 10
A method for improving the performance of a metal-air battery using high voltage is as described in example 1, except that: the active component used in the preparation of the positive plate is ZIF-67 derivative carbon modified by metal platinum nano particles, the solvent is Dimethylacetamide (DMAC), and the current collector is foam nickel; the metal salt used in preparing the electrolyte is LiN (CF) 3 SO 2 ) 2 The solvent is tetraethylene glycol dimethyl ether; the oxygen-containing gas was a mixture of 1% oxygen and 99% argon, and the pressure in the high-pressure vessel was 2000 atmospheres.
Example 11
A method for improving the performance of a metal-air battery using high voltage is as described in example 1, except that: the active component used in the preparation of the positive plate is metal palladium nano particles; the oxygen-containing gas was a mixture of 30% oxygen and 70% argon, and the pressure in the high-pressure vessel was 175 atm.
Example 12
A method for improving the performance of a metal-air battery using high voltage is as described in example 1, except that: the active component used in the preparation of the positive plate is RuO 2 Carbon nanotube mixture; the oxygen-containing gas was a mixed gas of 50% oxygen and 50% argon, and the pressure in the high-pressure vessel was 120 atm.
Example 13
A method for improving the performance of a metal-air battery using high voltage is as described in example 1, except that: the active component used in the preparation of the positive plate is graphene oxide, and the solvent is N, N-dimethylformamide; the solvent used for preparing the electrolyte is diethylene glycol dimethyl ether (DEGDME), and an oxidation-reduction initiator heme oxygenase is also added, wherein the concentration of the oxidation-reduction initiator in the electrolyte is 2mmol/L; the oxygen-containing gas was a mixture of 75% oxygen and 25% argon, and the pressure in the high-pressure vessel was 40 atmospheres.
Example 14
A method for improving the performance of a metal-air battery using high voltage is as described in example 1, except that: the current collector and the active component are cerium oxide modified graphene paper; the diaphragm is made of porous polypropylene film and the negative electrode is made of LiFePO when the battery is assembled 4 The method comprises the steps of carrying out a first treatment on the surface of the The oxygen-containing gas was a mixture of 5% oxygen and 95% neon, and the pressure in the high-pressure vessel was 1500 atmospheres.
Example 15
A method for improving the performance of a metal-air battery using high voltage is as described in example 1, except that: the battery anode is an integrated carbon nano tube film; the diaphragm used for assembling the battery is a graphene oxide film, and the inert protective atmosphere in the glove box is neon; the oxygen-containing gas was a mixture of 25% oxygen and 75% neon, and the pressure in the high-pressure vessel was 800 atmospheres.
Example 16
A method for improving the performance of a metal-air battery using high voltage is as described in example 1, except that: the battery anode is integrated graphene paper; the electrolyte is also added with a redox initiator which is tetrathiafulvalene (TTF), and the concentration of the redox initiator in the electrolyte is 10mmol/L; the oxygen-containing gas is a mixed gas of 50% oxygen and 50% neon, and the pressure in the high-pressure container is 250 atmospheres.
Example 17
A method for improving the performance of a metal-air battery using high voltage is as described in example 1, except that: the positive electrode of the battery is an integrated gold porous membrane; the inert protective atmosphere in the glove box is neon when the battery is assembled; the oxygen-containing gas was a mixture of 80% oxygen and 20% neon, and the pressure in the high-pressure vessel was 125 atmospheres.
Example 18
A method for improving the performance of a metal-air battery using high voltage is as described in example 1, except that: the battery anode is an integrated nickel porous membrane; and tetrabutylammonium chloride serving as an oxidation-reduction initiator is also added in the preparation of the electrolyte, wherein the concentration of the oxidation-reduction initiator in the electrolyte is 100mmol/L.
Example 19
A method for improving the performance of a metal-air battery using high voltage is as described in example 1, except that: the active component used in the preparation of the positive plate is carbon nano tube, and the current collector is carbon paper; a redox initiator triethyliodinated sulfur (TESI) was also added to the electrolyte at a concentration of 50mmol/L.
Example 20
A method for improving the performance of a metal-air battery using high voltage is as described in example 1, except that: the active component used in the preparation of the positive plate is conductive carbon black (Super P), and the current collector is carbon paper; the metal salt used for preparing the electrolyte is lithium perchlorate, the solvent is dimethyl sulfoxide (DMSO), and the oxidation-reduction initiator vanadyl acetylacetonate is also added during preparing the electrolyte, wherein the concentration of the oxidation-reduction initiator in the electrolyte is 5mmol/L.
Example 21
A method for improving the performance of a metal-air battery using high voltage is as described in example 1, except that: the adhesive used in the preparation of the positive plate is polytetrafluoroethylene, and the current collector is nickel screen; the metal salt used for preparing the electrolyte is lithium perchlorate, the solvent is dimethyl sulfoxide (DMSO), an oxidation-reduction initiator, namely dimethyl phenazine (DMPZ), is also added when preparing the electrolyte, and the additive, namely 1,2- (1, 2-tetrafluoroethoxy) ethane, wherein the concentration of the oxidation-reduction initiator in the electrolyte is 0.2mol/L, and the concentration of the additive is 0.1mol/L.
Example 22
A method for improving the performance of a metal-air battery using high voltage is as described in example 1, except that: the positive plate is an integrated gold porous film; when preparing electrolyte, adding an oxidation-reduction initiator ferrocene, wherein the concentration of the oxidation-reduction initiator in the electrolyte is 10mmol/L; the inert protective atmosphere in the glove box is neon when the battery is assembled.
Example 23
A method for improving the performance of a metal-air battery using high voltage is as described in example 1, except that: the positive plate is an integrated gold porous film; when preparing electrolyte, adding an oxidation-reduction initiator of dimethyl phenazine (DMPZ), and an additive of 1, 4-diazabicyclo [2, 2] octane (DABCO), wherein the concentration of the oxidation-reduction initiator in the electrolyte is 200mmol/L, and the concentration of the additive is 0.1mol/L; the oxygen-containing gas is a mixed gas of 20% oxygen and 80% argon, and the pressure in the high-pressure container is 80 atmospheres.
Example 24
A method for improving the performance of a metal-air battery using high voltage is as described in example 1, except that: the active component used in the preparation of the positive plate is a carbon nanotube; when preparing electrolyte, adding oxidation-reduction initiator N-Methyl Phenothiazine (MPT), wherein the concentration of the oxidation-reduction initiator in the electrolysis is 100mmol/L; the oxygen-containing gas is a mixed gas of 5% oxygen and 95% argon, and the pressure in the high-pressure container is 250 atmospheres.
Example 25
A method for improving the performance of a metal-air battery using high voltage comprising the steps of:
(1) Preparation of positive plate
Mn of 3 O 4 Uniformly mixing the nano particles with 5% of perfluorosulfonic acid (Nafion) aqueous solution, and Mn 3 O 4 The mass ratio of the nano particles to the perfluorinated sulfonic acid (Nafion) is 2:1, and the nano particles and the perfluorinated sulfonic acid (Nafion) are coated on a stainless steel net to lead Mn to be 3 O 4 The coating amount of the nano particles is 0.306mg/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the And (5) vacuum drying the positive plate, and then placing the positive plate into a glove box for standby.
(2) Preparation of electrolyte
Dissolving NaCl in deionized water, and fully stirring until the NaCl is completely dissolved to prepare NaCl solution with the concentration of 1.0 mol/L; then adding the additive graphene into the NaCl solution to enable the mass content of the additive graphene to reach 4wt%, and uniformly stirring to obtain the electrolyte.
(3) Battery assembly
The battery assembling process is completed in a glove box filled with high-purity argon; when the battery is assembled, the battery component is arranged in the battery shell according to the sequence of the positive plate immersed by the electrolyte, the polyethylene diaphragm and the magnesium plate, and the battery is pressed by a press.
(4) High voltage treatment of batteries
In the glove box, the assembled battery is put into a high-pressure container, and the battery is sealed after the test electrode is connected. Taking the high-pressure container out of the glove box, connecting a high-pressure gas path, and connecting a test electrode to test equipment; the high-pressure gas is provided by a high-pressure gas steel cylinder or a high-pressure gas control device.
Filling oxygen-containing gas into the high-pressure container until the pressure in the high-pressure container reaches 80 atmospheres, then maintaining constant pressure and standing for 2.5 hours to ensure that the battery reaches a stable state; the oxygen-containing gas is compressed air.
Example 26
A method for improving the performance of a metal-air battery using high voltage is described in example 25, except that: the active component used in the preparation of the positive plate is conductive carbon black, the binder is polyvinylidene fluoride (PVDF), and the current collector is carbon fiber cloth; the metal salt used for preparing the electrolyte is Mg (NO 3 ) 2 The solvent is trihexyl (tetradecyl) phosphine chloride; the battery negative plate is Ni-Mg alloy; the pressure in the high pressure vessel was 200 atmospheres.
Example 27
A method for improving the performance of a metal-air battery using high voltage is described in example 25, except that: the active component is platinum-carbon alloy; the metal salt used for preparing the electrolyte is NaNO 3 The negative electrode of the battery is made of magnesium-aluminum-lead alloy; the pressure in the high pressure vessel was 300 atmospheres.
Example 28
A method for improving the performance of a metal-air battery using high voltage is described in example 25, except that: the active component used in the preparation of the positive plate is graphene; the pressure in the high pressure vessel was 450 atmospheres.
Example 29
A method for improving the performance of a metal-air battery using high voltage is described in example 25, except that: the active component used in the preparation of the positive plate is a carbon nanotube; the separator used in assembling the battery is ZrO 2 A solid electrolyte membrane.
Example 30
A method for improving the performance of a metal-air battery using high voltage is described in example 25, except that: the active component used in preparing the positive plate is platinum-magnesium alloy, the oxygen-containing gas is oxygen, and the pressure in the high-pressure container is 50 atmospheres.
Example 31
A method for improving the performance of a metal-air battery using high voltage is described in example 25, except that: the oxygen-containing gas was oxygen and the pressure in the high pressure vessel was 350 atmospheres.
Example 32
A method for improving the performance of a metal-air battery using high voltage comprising the steps of:
(1) Preparation of positive plate
Uniformly mixing acetylene black, polytetrafluoroethylene slurry (solid content is 60%) and conductive carbon black in ethanol according to a mass ratio of 4:4:2, and then pressing into a sheet with a thickness of 0.2-0.3 mm; then, mixing acetylene black and polytetrafluoroethylene slurry according to a weight ratio of 1:4, and pressing into a sheet with a thickness of 0.3 mm; and (3) carrying out hot pressing on the two obtained sheets and carbon paper together under the pressure of 20MPa, and carrying out vacuum drying at 80 ℃ to obtain the positive plate with the three-layer structure.
(2) Preparation of electrolyte
KOH is dissolved in deionized water and fully stirred until the KOH is completely dissolved to prepare KOH solution with the concentration of 8.0 mol/L; then, adding an additive NaSnO into the KOH solution 3 And In (OH) 3 The concentrations of the electrolyte are respectively 0.02 mmol/L and 0.8mmol/L, and the electrolyte is obtained after uniform stirring;
(3) Battery assembly
The battery assembling process is completed in a glove box filled with high-purity argon; when the battery is assembled, the battery component is arranged in the battery shell according to the sequence of the positive plate soaked by electrolyte, the porous polypropylene fiber film and the aluminum sheet, and the battery is pressed by a press.
(4) High voltage treatment of batteries
The assembled battery is put into a high-voltage container, and the battery is sealed after the test electrode is connected. Taking the high-pressure container out of the glove box, connecting a high-pressure gas path, and connecting a test electrode to test equipment; the high-pressure gas is provided by a high-pressure gas steel cylinder or a high-pressure gas control device.
Filling oxygen-containing gas into the high-pressure container through the high-pressure gas path until the pressure in the high-pressure container is 80 atmospheres, then maintaining a constant pressure and standing for 2.5 hours to enable the battery to reach a stable state; the oxygen-containing gas is compressed air.
Example 33
A method for improving metal-air battery performance using high voltage is described in example 32, except that: the active component used in the preparation of the positive plate is carbon black, and the current collector is foam nickel; the metal salt used in preparing the electrolyte is NaCl, the additive is Cetyl Trimethyl Ammonium Bromide (CTAB), and the concentration of the additive in the electrolyte is 0.03mol/L; the negative electrode of the battery adopts aluminum-magnesium-tin alloy; the pressure in the high pressure vessel was 150 atmospheres.
Example 34
A method for improving metal-air battery performance using high voltage is described in example 32, except that: active components used in preparing the positive plate are active carbon, and the current collector is a copper mesh; the metal salt used in preparing electrolyte is NaOH and the additive is KNaC 4 H 4 O 6 The concentration of the additive in the electrolyte is 1mol/L; an aluminum sheet is adopted as a battery cathode; the pressure in the high pressure vessel was 1200 atmospheres.
Example 35
A method for improving metal-air battery performance using high voltage is described in example 32, except that: the active component used in the preparation of the battery positive plate is a mixture of active carbon and acetylene black, and the current collector is nickel screen; the electrolyte additive is NaSnO 3 And ZnO, wherein the concentration of the additive in the electrolyte is 0.01mol/L and 0.0075mol/L respectively; an aluminum sheet is adopted as a battery cathode; the pressure in the high pressure vessel was 350 atmospheres.
Example 36
A method for improving metal-air battery performance using high voltage is described in example 32, except that: the active component used in the preparation of the battery positive plate is a mixture of carbon black and acetylene black, and the current collector is foam nickel; the gas was compressed air during cell testing and the pressure in the high pressure vessel was 650 atmospheres.
Example 37
A method for improving metal-air battery performance using high voltage is described in example 32, except that: the oxygen-containing gas was oxygen, and the pressure in the high-pressure vessel was 250 atmospheres.
Example 38
A method for improving the performance of a metal-air battery using high voltage is as described in example 31, except that: the oxygen-containing gas was 2% oxygen+98% argon, and the pressure in the high-pressure vessel was 1500 atmospheres.
Example 39
A method for improving the performance of a metal-air battery using high voltage comprising the steps of:
(1) Preparation of positive plate
Dispersing N-doped graphene in 5% perfluorosulfonic acid (Nafion) isopropanol solution to make the mass ratio of the N-doped graphene to the perfluorosulfonic acid be 3:1, uniformly stirring, and then coating the mixture on the surface of foam nickel to make the coating amount of the N-doped graphene be 6mg/cm 2 And (5) drying in vacuum at 80 ℃ to obtain the required positive plate.
(2) Preparation of electrolyte
KOH is dissolved in deionized water and fully stirred until the KOH is completely dissolved to prepare KOH solution with the concentration of 6.0 mol/L; next, znCl is added to the KOH solution 2 The concentration is made to be 0.2mol/L, and the required electrolyte is obtained after uniform stirring.
(3) Battery assembly
The battery assembling process is completed in a glove box filled with high-purity nitrogen; when in assembly, the battery component is put into the battery shell according to the sequence of the positive plate soaked by electrolyte, the porous polypropylene fiber film and the zinc plate, and then the battery is pressed by a press.
(4) High voltage treatment of batteries
The assembled battery is put into a high-voltage container, and the battery is sealed after the test electrode is connected. Taking the high-pressure container out of the glove box, connecting a high-pressure gas path, and connecting a test electrode to test equipment; the high-pressure gas is provided by a high-pressure gas steel cylinder or a high-pressure gas control device.
Filling oxygen-containing gas into the high-pressure container through the high-pressure gas path until the pressure in the high-pressure container is 80 atmospheres, then maintaining constant pressure and standing for two hours to ensure that the battery reaches a stable state; the oxygen-containing gas is compressed air.
Example 40
A method for improving metal-air battery performance using high voltage is described in example 39, except that: the active component used in the preparation of the positive plate is carbon black, the solvent is ethanol, the binder is polyvinylidene fluoride (PVDF), and the current collector is carbon paper; the pressure in the high pressure vessel was 240 atmospheres.
Example 41
A method for improving metal-air battery performance using high voltage is described in example 39, except that: active components used in the preparation of the positive plate are activated carbon, a binder is Polytetrafluoroethylene (PTFE), and a current collector is carbon paper; the metal salt added in the preparation of the electrolyte is zinc acetate; the pressure in the high pressure vessel was 120 atmospheres.
Example 42
A method for improving metal-air battery performance using high voltage is described in example 39, except that: the oxygen-containing gas was oxygen, and the pressure in the high-pressure vessel was 165 atmospheres.
Example 43
A method for improving metal-air battery performance using high voltage is described in example 38, except that: the oxygen-containing gas was 55% oxygen+45% argon, and the pressure in the high-pressure vessel was 220 atmospheres.
Claims (17)
1. A method for improving the performance of a metal-air battery using high voltage comprising the steps of:
and placing the metal-air battery in a high-pressure container, filling oxygen-containing gas into the high-pressure container until the pressure in the high-pressure container is 15-2000 atm, maintaining constant pressure, and standing for 2-6 hours.
2. The method of claim 1, wherein the metal-air battery is a lithium-oxygen battery, a magnesium-air battery, a magnesium-oxygen battery, an aluminum-air battery, an aluminum-oxygen battery, a zinc-air battery, or a zinc-oxygen battery.
3. The method of claim 1, wherein the oxygen-containing gas is oxygen, an oxygen-nitrogen mixture, an oxygen-argon mixture, an oxygen-neon mixture, or compressed air.
4. The method of claim 1, wherein the oxygen-containing gas is oxygen or an oxygen-argon mixture.
5. The method of improving the performance of a metal-air battery of claim 1, wherein the oxygen-containing gas has a volume content of oxygen of 1 to 100%.
6. The method of improving the performance of a metal-air battery of claim 1, wherein the oxygen-containing gas has a volume content of oxygen of 20 to 100%.
7. The method of improving the performance of a metal-air battery of claim 1, wherein the oxygen-containing gas has a volume content of oxygen of 60 to 100%.
8. The method for improving the performance of a metal-air battery according to claim 1, wherein the oxygen-containing gas is filled to a pressure of 20 to 1000 atmospheres in the high-pressure vessel.
9. The method for improving the performance of a metal-air battery according to claim 1, wherein the oxygen-containing gas is filled to a pressure of 30 to 600 atm in the high-pressure vessel.
10. The method for improving the performance of a metal-air battery according to claim 1, wherein the oxygen-containing gas is filled to a pressure of 30 to 300 atm in the high-pressure vessel.
11. The method for improving the performance of a metal-air battery according to claim 1, wherein the partial pressure of oxygen reaches 10 to 200 atm when the high-pressure vessel is filled with the oxygen-containing gas; the time for maintaining constant pressure was 2.5 hours.
12. The method for improving the performance of a metal-air battery according to claim 1, wherein the partial pressure of oxygen reaches 40 to 100 atm when the high-pressure vessel is filled with the oxygen-containing gas.
13. The method for improving the performance of a metal-air battery according to claim 1, wherein the metal-air battery is prepared according to the following method:
(1) Preparation of positive plate
The preparation is carried out by one of the following methods:
adding the active component and the binder into the solvent according to the mass ratio of 2:1-9:1, wherein the mass ratio of the active component to the volume of the solvent is 20-200mg:1mL, uniformly stirring to obtain a mixture, coating the mixture on a current collector, and the coating amount of the active component is 0.1-10mg/cm 2 Vacuum drying for later use; or (b)
Ii, directly vacuum drying the integrated electrode to prepare an electrode sheet for later use; or (b)
Adding the active component, the binder slurry and the conductive carbon black into a solvent according to the mass ratio of 1-4.5:1-4.5:1, wherein the mass ratio of the active component to the solvent is 20-200mg:1mL, stirring uniformly, and pressing into a sheet with the thickness of 0.2-0.3 mm; uniformly mixing the active component and the binder slurry according to the mass ratio of 1:1-1:9, and pressing into a sheet with the thickness of 0.3 mm; hot-pressing the two obtained thin sheets and a current collector together, and then drying in vacuum to obtain a positive plate with a three-layer structure; the solid content of the binder slurry is 60wt%;
(2) Preparation of electrolyte
Adding metal salt, an additive and an oxidation-reduction initiator into a solvent, and stirring until the metal salt, the additive and the oxidation-reduction initiator are completely dissolved to obtain electrolyte with the metal salt concentration of 0.1-10.0 mol/L;
(3) Battery assembly
And (3) sequentially loading the positive electrode plate soaked by the electrolyte, the diaphragm soaked by the electrolyte and the metal negative electrode plate into a battery shell, and compacting by a press to obtain the metal-air battery.
14. The method of improving the performance of a metal-air battery of claim 13, wherein step (1) comprises one or more of the following conditions:
a. the active components are one or more than two of acetylene black, active carbon, graphene, doped graphene, graphene oxide, carbon nano tube, conductive carbon black, noble metal and oxides thereof, transition metal oxide, rare earth metal oxide and platinum-magnesium alloy; the noble metal is ruthenium, gold, platinum or palladium; the transition metal oxide is Mn 3 O 4 Cobalt oxide, iron oxide; the rare earth metal oxide is cerium dioxide;
b. the binder is perfluorosulfonic acid, polyvinylidene fluoride or polytetrafluoroethylene;
c. the solvent is one or the combination of more than two of ethanol, isopropanol, N-methylpyrrolidone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide and water;
d. the current collectors are carbon paper, carbon fiber cloth, graphene paper, nickel mesh, stainless steel mesh, copper mesh, foam nickel, noble metal porous membrane or carbon nanotube membrane; the noble metal porous membrane is a porous gold membrane, a porous silver membrane or a porous platinum membrane;
e. the integrated electrode is an electrode with the active component and the current collector in the same species, and is one of graphene paper, ceria modified graphene paper, graphene oxide paper, a carbon nanotube film, a noble metal porous net, a transition metal porous film and a transition metal porous net; the noble metal is gold, platinum or silver; the transition metal is nickel, titanium or iron.
15. The method of improving the performance of a metal-air battery of claim 13, wherein step (2) comprises one or more of the following conditions:
a. the metal salt is LiClO 4 、LiCF 3 SO 3 、LiN(CF 3 SO 2 ) 2 、Mg(NO 3 ) 2 、NaNO 3 One or more than two of NaOH, KOH, zinc acetate, liBr, liI, naCl, naBr, zinc chloride and zinc oxide;
b. the solvent is dimethyl sulfoxide, N-dimethylformamide, dimethyl ether triethylene glycol, tetraethylene glycol dimethyl ether, diethylene glycol dimethyl ether, CH 3 One or more of CN, trihexyl (tetradecyl) phosphine chloride and water;
c. the additive is 1-methoxy-2- (1, 2-tetrafluoroethoxy) ethane, 1, 4-diazabicyclo [2, 2)]Octane, water-soluble graphene, na 2 SnO 3 、In(OH) 3 Zinc oxide, zinc chloride, cetyltrimethylammonium bromide, KNaC 4 H 4 O 6 One or a combination of two or more of them; the additive is 1-methoxy-2- (1, 2-tetrafluoroethoxy) ethane and 1, 4-diazabicyclo [2, 2)]Octane, na 2 SnO 3 、In(OH) 3 Zinc oxide, zinc chloride, cetyltrimethylammonium bromide, KNaC 4 H 4 O 6 When one or more than two of the above are combined, the concentration of the additive in the electrolyte is 0-2.0mol/L;
d. the oxidation-reduction initiator is one or more than two of tetrabutylammonium chloride, vanadyl acetylacetonate, triethyliodized sulfur, tetrathiafulvalene, ferrocene, dimethyl phenazine, tris [4- (diethylamino) phenyl ] amine, heme oxygenase, N-methyl phenothiazine and 2, 6-tetramethyl piperidine oxide; the concentration of the oxidation-reduction initiator in the electrolyte is 0-500.0mmol/L.
16. The method for improving the performance of a metal-air battery according to claim 15, wherein when the additive in the step (2) is water-soluble graphene, the mass concentration of the additive in the electrolyte is 0-5wt%.
17. The method of improving the performance of a metal-air battery of claim 13, wherein step (3) comprises one or more of the following conditions:
a. the diaphragm is a glass fiber film, a graphene oxide film, a porous polypropylene fiber film and ZrO 2 A solid electrolyte membrane, polyethylene oxide or polyethylene film;
b. the metal negative plate is a lithium plate and LiFePO 4 Metal magnesium sheet, magnesium alloy, metal aluminum sheet, aluminum alloy or metal zinc sheet; the magnesium alloy is an alloy of magnesium and one or more than two of aluminum, tin, nickel and lead; the aluminum alloy is an alloy of aluminum and one or more than two of magnesium, tin and cerium;
c. the assembly of the battery needs to be performed in a glove box, and the protective gas in the glove box is nitrogen, argon or neon.
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