US20180366737A1 - Composite air electrode and associated manufacturing method - Google Patents

Composite air electrode and associated manufacturing method Download PDF

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US20180366737A1
US20180366737A1 US16/060,257 US201616060257A US2018366737A1 US 20180366737 A1 US20180366737 A1 US 20180366737A1 US 201616060257 A US201616060257 A US 201616060257A US 2018366737 A1 US2018366737 A1 US 2018366737A1
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porous structure
fluoropolymer
air
membrane
electrode
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Philippe Stevens
Gwenaelle Toussaint
Sophie Deshayes
Silvia Rita PETRICCI
Padmanabhan Srinivasan
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Syensqo SA
Electricite de France SA
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Solvay SA
Electricite de France SA
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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
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
    • 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
    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
    • 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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/24—Electrodes for alkaline accumulators
    • H01M4/244—Zinc electrodes
    • 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
    • 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
    • H01M4/8605—Porous electrodes
    • 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
    • H01M4/88—Processes of manufacture
    • H01M4/8803—Supports for the deposition of the catalytic active composition
    • H01M4/881—Electrolytic membranes
    • 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
    • H01M4/96—Carbon-based electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/145—Cells with non-aqueous electrolyte containing ammonia
    • 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
    • H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
    • H01M2004/8689—Positive electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • H01M2300/0014—Alkaline electrolytes
    • 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
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention relates to the field of protecting the air electrode of a metal-air electrochemical cell against the corrosive effects of a liquid electrolyte of basic pH. It may have applications in zinc-air batteries.
  • Electrochemical cells are generally composed of a negative electrode, a positive electrode, and an electrolyte for the transit of charge carriers from one electrode to the other.
  • Metal-air electrochemical cells generally comprise a liquid electrolyte.
  • the negative electrode typically formed from a metal compound M, decomposes into M n+ ions during discharge while oxygen from the air is reduced at the positive electrode, called the air electrode, in the following reactions:
  • One of the advantages of metal-air systems is the use of a positive electrode, also called an air electrode, of infinite capacity.
  • the oxygen consumed at the positive electrode does not need to be stored in the electrode but can be taken from the surrounding air
  • Metal-air electrochemical generators are thus known for their high specific energy, which can reach several hundreds of Wh/kg.
  • Air electrodes are used for example in alkaline fuel cells, which are particularly advantageous compared to other systems because of the high reaction kinetics at the electrodes and the absence of noble metals such as platinum.
  • metal-air cells are based on the use of a non-alkali metal such as zinc in the negative metal electrode.
  • a zinc electrode is stable in an alkaline electrolyte.
  • Metal-air batteries, particularly zinc-air batteries, are found for example in hearing aids.
  • An air electrode is a porous solid structure, usually of carbon grains, in contact with the liquid electrolyte.
  • the interface between the air electrode and the liquid electrolyte is a “triple contact” interface where the active solid material of the electrode, the gaseous oxidant, meaning oxygen from the air, and the liquid electrolyte are present simultaneously.
  • a description of the different types of air electrodes for zinc-air batteries is provided for example by Neburchilov V. et al. in the article entitled “A review on air cathodes for zinc-air fuel cells”. Journal of Power Sources 195 (2010) p 1271-1291.
  • air electrodes degrade quickly, even when not in operation, in particular because of the corrosive effect of the liquid electrolyte of basic pH of the electrochemical cells.
  • the liquid electrolyte can dissolve the constituent catalyst of the air electrode.
  • the cations from the dissolved catalyst may contribute to degrading the performance of a metal-air cell, by facilitating an undesirable water reduction reaction likely to interfere with the deposition of metal on the negative electrode, reduce the Coulomb and energy efficiency, and consume the water.
  • metal zinc is deposited by electrochemical reduction on the negative electrode of the battery, from an aqueous solution of zincate ions. It turns out that the theoretical reduction potential of zincate ion to metal zinc is less negative than the theoretical reduction potential of water to hydrogen. Both reactions can coexist at the negative electrode.
  • An overvoltage at the zinc negative electrode facilitates the zincate reduction reaction over the water reduction, but is insufficient to prevent the water reduction, particularly in the presence of ion impurities from a deteriorated air electrode.
  • peroxide is known to degrade the polymer electrolytes likely to be used in a fuel cell.
  • the carbon dioxide present in air diffuses into the concentrated basic solution and is converted into carbonate anion, which precipitates in the presence of cations.
  • the low solubility of the formed carbonates leads to progressive carbonatation of the electrolyte.
  • Document FR0953021 proposes protecting an air electrode of a metal-air battery by using an interpenetrating polymer network (IPN) or a semi-interpenetrating polymer network (semi-IPN) Uncured network is deposited on the air electrode and then solidified in situ by polymerization.
  • IPN interpenetrating polymer network
  • Si-IPN semi-interpenetrating polymer network
  • Uncured network is deposited on the air electrode and then solidified in situ by polymerization.
  • the semi-IPN or IPN network is attached by anchoring the polymer in the pores of the air electrode over a thickness typically corresponding to 2% of the thickness of the electrode.
  • a membrane of IPN or non-fluorinated semi-IPN is not impermeable to highly concentrated basic electrolytes, and degrades in an electrolyte comprising a hydroxyl ion concentration of around 8 mol/L or higher.
  • the present invention provides a method for manufacturing a composite electrode intended for use in a metal-air electrochemical cell with a liquid electrolyte of basic pH, the method comprising:
  • the invention relies on a method which does not perform in situ polymerization in order to form a protective membrane on the air electrode of a metal-air cell.
  • the method of the invention also does not require anchoring the polymer in the pores of an air electrode. This reduces the thickness of the polymer membrane deposited on the surface, without impacting its impermeability. Indeed, as the fluoropolymer is already polymerized, in the form of a suspension in the first liquid solution, it does not penetrate, or barely penetrates, the pores of the air electrode and advantageously remains trapped on the outer surface of the latter, while the solvent of the first liquid solution flows through the pores of the air electrode.
  • the polymer trapped on the outer surface of the air electrode will naturally aggregate to form a thin protective layer which is impermeable to a basic liquid electrolyte.
  • the choice of fluoropolymer to obtain the desired effect of hydroxyl ion conduction and impermeability can concern compositions such as those described in WO2012/098146.
  • the method of the present invention allows depositing a thinner polymer layer than methods of the prior art, without losing impermeability to the liquid electrolyte.
  • the thickness of a protective layer for the electrode has a thickness chosen as a compromise between acting as a barrier to the liquid electrolyte and good conductance.
  • a protective layer according to the prior art is typically with a sufficient thickness to avoid holes and to form an effective barrier against the liquid electrolyte, although this is at the expense of conductance.
  • the resistivity of a protective layer increases with thickness. The method of the invention facilitates obtaining a hole-free layer of low thickness, thus forming an impermeable barrier to the liquid electrolyte without increasing the resistivity of the protective layer in comparison to methods of the prior art.
  • the air electrode is no longer directly exposed to the corrosive basic medium of the liquid electrolyte. Thus, the phenomena of flooding the air electrode and dissolution of the air electrode catalyst can be avoided.
  • the method may further comprise:
  • the implementation of a composite electrode according to the method described above can be performed by a single application of the first liquid solution, with no solvent evaporation step.
  • the solvent can flow through the pores of the air electrode.
  • the first liquid solution is applied multiple times onto the air electrode, typically two or three times, it may be advantageous to add a solvent evaporation step. The solvent can no longer flow naturally through the air electrode pores, when access to these pores is blocked by the previously applied polymer layer.
  • the method further comprises, during the obtaining of the porous structure:
  • the porous structure of the air electrode comprises the polymer conductive to hydroxyl ions that is impermeable to the liquid electrolyte, distributed in the volume of the air electrode, preferably uniformly.
  • the porous structure of the composite electrode thus obtained is effectively protected against any basic electrolyte which successfully crosses the membrane covering the outer surface of the air electrode.
  • this embodiment also can significantly reduce the carbonatation phenomenon in the composite electrode. By incorporating the fluoropoly mer into the electrode structure, the reduction of the carbonatation phenomenon is even more pronounced.
  • the electrode may be intended for a metal-air battery as a positive electrode, the pH of the liquid electrolyte being about 14 or higher.
  • the polymer membrane obtained by the method described above forms an effective seal against highly concentrated basic electrolytes having a pH greater than 14 and which typically can reach hydroxyl ion concentrations of around 8 mol/L or higher.
  • the invention also relates to a composite electrode intended for use in a metal-air electrochemical cell with a liquid electrolyte of basic pH, the composite electrode comprising:
  • the fluoropolymer of the composite electrode comprises SO 2 N groups facilitating the conduction of hydroxyl ions through the membrane.
  • the SO 2 N group may be part of a SO 2 NRQ + group where:
  • the fluoropolymer described above may correspond to or comprise a compound such as the one described in document WO2012/098146.
  • the fluoropolymer comprises a fluorinated backbone chain with polar groups that are at least partially hydrogenated.
  • a fluoropolymer comprising a fluorinated backbone and at least partially hydrogenated polar groups has the property of naturally forming thin layers by the method described above. According to one possible explanation of this phenomenon, provided as an illustrative and non-limiting example, it seems that the at least partially hydrogenated polar groups of the polymer contribute both to binding the polymer aggregates together after application onto the outer surface of the air electrode, and binding themselves to the outer surface of the air electrode without significantly penetrating into the pores of the surface.
  • the fluoropolymer further comprises at least one quaternary ammonium group with no hydrogen in the beta position.
  • the fluoropolymer comprises groups belonging to the family of tetrafluoroethylene and sulfur groups.
  • the thickness of the protective membrane can be between 10 ⁇ m and 100 ⁇ m.
  • Such a thickness allows obtaining a composite electrode of which the protective polymer membrane is simultaneously sufficiently impermeable to a basic electrolyte, has sufficient mechanical strength at the membrane, and sufficiently conducts hydroxyl ions across the membrane. Good mechanical strength combined with good ion conduction gives satisfactory electrical performance to an electrochemical cell equipped with a composite electrode according to the invention.
  • the porous structure comprises a polymer-based material optimizing the conduction of hydroxyl ions.
  • the polymer-based material of the porous structure can form an interpenetrating polymer network or a semi-interpenetrating polymer network.
  • the hydroxyl ions can move more easily from the electrolyte to the porous structure and occupy as much of the volume of the air electrode as possible. It is thus possible to obtain an air electrode providing particularly efficient oxygen reduction, exploiting the full volume of the electrode.
  • the invention also relates to a metal-air battery comprising a composite electrode as described above.
  • the battery may further comprise a metal negative electrode of zinc and a liquid electrolyte of a basic pH of about 14 or higher.
  • FIG. 1 is a schematic representation of a metal-air electrochemical cell comprising a composite electrode according to the invention
  • FIGS. 2 a and 2 b are schematic representations of the application of a first liquid solution comprising a fluoropolymer capable of forming a layer impermeable to a liquid electrolyte of basic pH, onto a porous structure:
  • FIG. 3 is a schematic representation of a composite electrode according to a first embodiment in a liquid electrolyte of high basic pH, illustrating the conductive and barrier properties of the electrode in discharge phase:
  • FIG. 4 is a schematic representation of a composite electrode according to a second embodiment, in discharge phase.
  • FIG. 5 is a graph comparing the service life in hours with untreated ambient air, of a standard air electrode of the prior art, to that of a composite air electrode according to the present invention, in two solutions of high hydroxyl ion concentrations.
  • FIG. 1 shows a metal-air electrochemical cell 10 comprising a composite electrode which is an object of the present invention, obtainable by the method presented below.
  • the cell represented in FIG. 1 may be an integral part of a metal-air battery comprising a plurality of electrochemical cells. It is also possible for a battery to comprise only one cell.
  • the electrochemical cell 10 comprises two composite electrodes 1 , corresponding to air electrodes having a porous structure 7 .
  • the porous structure 7 of an air electrode of an electrochemical cell can be obtained from carbon grains 6 joined by a binder. The space between the carbon grains 6 allows air and in particular oxygen contained in the air to flow through the porous structure 7 to a triple interface of air/electrode/OH ⁇ ions. This triple interface is the site of oxidation reactions.
  • the porous structure 7 comprises, on an outer surface facing a liquid electrolyte, a membrane 8 impermeable to the liquid electrolyte 3 of basic pH.
  • the liquid electrolyte may advantageously contain a low concentration of H + ions and have a pH of about 14 or higher.
  • high pH values can be expressed in concentrations of OH ⁇ ions.
  • a high concentration of OH ⁇ ions can offer better electrical performance by allowing a larger number of OH ⁇ ions to reach the reaction site at the triple interface of the porous structure.
  • the liquid electrolyte 3 typically comprises a high concentration of OH ⁇ ions, also known as hydroxyl ions 4 , and also comprises M n+ metal ions 5 , as shown in FIG. 1 .
  • the OH ⁇ ions can freely pass through the membrane 8 .
  • the membrane 8 is impermeable to the other species present in the electrolyte 3 and in particular can advantageously prevent direct contact of the electrolytic liquid with the porous structure 7 .
  • the flooding phenomenon observed in air electrodes can be avoided as can the corrosive effect of the electrolyte 3 on the porous structure 7 .
  • the membrane 8 is composed of a fluoropolymer deposited on the outer surface of the porous structure 7 .
  • FIGS. 2 a and 2 b schematically represent the deposition of the polymer as a layer 22 .
  • This layer 22 is formed on the outer surface 25 of the porous structure 7 without having to penetrate inside the pores.
  • a first liquid solution 20 is prepared.
  • This liquid solution comprises a fluoropolymer 9 suspended in a solvent 21 .
  • the fluoropolymer 9 shown in FIG. 2 a is composed of molecules in the form of long polymer chains.
  • the representation as fibers in FIGS. 2 a and 2 b illustrates the fact that the fluoropolymer 9 is present in the solvent 21 in polymerized form. However, at this stage these polymer chains do not yet form an assembled semi-rigid ensemble.
  • the solvent 21 flows through the pores of the porous structure 7 between the carbon grains 6 , for example following paths 23 as shown in FIG. 2 b .
  • the molecules of elongate structure of the fluoropolymer 9 penetrate the porous structure 7 with difficulty.
  • the fluoropolymer 9 is retained on the outer surface 25 of the porous structure. This retention on the outer surface without penetrating the pores of the air electrode is related to the length of the fluoropolymer chains 9 , already polymerized at the time of application of the liquid solution onto the porous structure, and is related to the composition of the porous structure 7 itself.
  • porous structures 7 used in metal-air electrochemical cells generally comprise polytetrafluoroethylene (PTFE). It has been noted that PTFE seems to have a repellent effect on the fluoropolymer 9 , facilitating its retention on the outer surface 25 of an air electrode.
  • PTFE polytetrafluoroethylene
  • Deposition of the first fluid solution 20 onto the outer surface 25 of the porous structure 7 may for example be done by painting, transfer, and may involve the use of a scraper to spread the polymer.
  • the solvent 21 flows through the porous structure while the polymer chains of the fluoropolymer 9 are filtered and retained on the outer surface 25 of the porous structure. Due to this filtering, the molecules of the fluoropolymer are no longer dispersed in the solvent and their clumping on the outer surface 25 of the porous structure facilitates their aggregation to form an impermeable structure in the form of a layer 22 .
  • the process of consolidation of the layer 22 can occur without outside intervention once the fluoropolymer 9 is deposited on the porous structure 7 . Aggregation of the polymer chains to form the layer 22 may be accelerated, however, by exposing the structure of FIG. 2 b to a temperature higher than room temperature.
  • the stability of the contact between the layer 22 and the outer surface of the porous structure could be attributed to adhesion of the fluoropolymer 9 to the outer surface 25 of the porous structure.
  • the air electrode due to its porous structure, the air electrode has an outer surface having numerous irregularities which increase the surface area of this surface. Low forces of adhesion, such as Van der Waals forces, can provide sufficient attraction to maintain the layer 22 in a fixed position in contact with the porous structure 7 .
  • carboxyl groups typically contained in the grains 6 of the porous structure 7 of an air electrode also contribute to maintaining the fluoropoly mer in contact with the outer surface 25 .
  • the method for depositing the fluoropolymer 9 on the outer surface of the porous structure 7 can be performed all at once as schematically Illustrated in FIGS. 2 a and 2 b . However, it may also be carried out in multiple applications, typically two or three, to obtain a greater thickness of the membrane 8 .
  • membrane 8 thicknesses between 10 ⁇ m and 100 ⁇ m.
  • Such a thickness range makes it possible to ensure sufficient impermeability to the strongly basic liquid electrolyte 3 , as well as effective conduction of hydroxyl ions 4 through the membrane 8 and sufficient mechanical strength of the membrane.
  • the method for forming a membrane 8 according to the invention has the advantage of facilitating the formation of an impermeable layer of low thickness, without holes.
  • the obtained membrane 8 forms an effective barrier to the liquid electrolyte while offering a conductance which is not reduced by the thickness of the membrane. Indeed, as mentioned above, membrane resistivity increases with thickness. A reduction in the thickness therefore contributes to increasing the conductance.
  • an additional step of solvent 21 evaporation can be implemented after a first application of the first liquid solution. This evaporation may be achieved by heating the solvent, for example at temperatures between room temperature and 100° C., preferably a temperature of 80° C.
  • FIG. 3 schematically shows a portion of a composite electrode of a metal-air cell.
  • the porous structure 7 comprises on its outer surface a membrane 8 of fluoropolymer 9 , aggregated into a layer impermeable to the liquid electrolyte 3 .
  • the hydroxyl ions OH ⁇ can pass through the membrane 8 .
  • the fluoropolymer present as a layer on the outer surface of the porous structure, forms a barrier to the liquid electrolyte having a high concentration of hydroxyl ions, it was found that this layer also reduces the carbonatation phenomenon in the composite electrode by preventing direct contact between the CO 2 from the air and the liquid electrolyte.
  • the fluoropolymer does not appear to have the intrinsic property of total impermeability to carbon dioxide, its use in combination with the porous structure of the air electrode appears to result in slowing down the carbon dioxide diffusion phenomenon in the composite electrode.
  • the fluoropolymer is chosen so as to possess such multiple properties combining impermeability to a liquid electrolyte 3 and conduction of hydroxyl ions.
  • polymers comprising SO 2 N groups have hydroxyl ion conduction properties enabling metal-air batteries to provide satisfactory electrical performance.
  • the radical R may typically be selected from hydrogen, an alkyl of the C 1 -C 20 group, a cyclic compound comprising the Q+ group and between 2 and 20 carbon atoms, and a cyclic compound comprising the Q+ group, between 2 and 20 carbon atoms, and up to 4 heteroatoms.
  • SO 2 NRQ + compounds suitable for the composite electrode of the invention can be obtained according to the methods described in WO 2012/098146.
  • the deposition method of the invention allows obtaining a protective membrane 8 which adheres to the outer surface 25 of a porous structure 7 without having to penetrate the pores of the air electrode to ensure stable anchoring to the electrode.
  • This surprising stability further enables oxygen to make maximum use of the volume of the porous structure for oxidation reactions.
  • the hydroxyl ions 4 can freely migrate through the membrane 8 as indicated by the path 40 in FIG. 3 , to reach the pores between the grains 6 of the porous structure 7 where oxygen from the air is also located.
  • the oxygen O 2 can also migrate freely in the pores of the air electrode as indicated by the path 20 in FIG. 3 .
  • the hydroxyl ions and oxygen can thus interact in a maximized number of reaction sites throughout the volume of the air electrode.
  • the reaction volume available for oxidation reactions is not reduced by flooding phenomena, prevented by the presence of the impermeable membrane, or by the fluoropolymer 9 which does not fill the pores of the air electrode, even in the superficial areas of the latter.
  • the adhesion of the membrane 8 to the outer surface 25 of the porous structure 7 can be optimized when the fluoropolymer 9 comprises a backbone chain with at least one polar group and/or at least one group that is at least partially hydrogenated.
  • Polar groups can interact with the carbon contained in an air electrode.
  • the presence of sulfur groups on the backbone chain of the fluoropolymer 9 may also contribute to an interaction with the air electrode in a way that facilitates organization of the fluoropolymer 9 into a layer on the outer surface 25 of a porous structure 7 .
  • the membrane 8 comprising the fluoropolymer as a layer 9 has a higher resistance to alkaline electrolytes with high hydroxyl ion concentrations than membranes based on interpenetrating polymer or semi-interpenetrating polymer networks such as those described in document FR0953021.
  • This improved resistance can be attributed to the addition of a backbone chain comprising the fluoropolymer, in the quaternary anmmonium group.
  • quaternary ammonium groups are not known to be stable in strongly basic solutions, it has been found that by using a diamine containing no hydrogen in the beta position of the quaternary ammonium group, a particularly satisfactory stability and resistance can be obtained.
  • fluoropolymer that can be used in the invention is described below.
  • Such a polymer consists of a carbon backbone chain comprising groups associated thereto by covalent bonds. These groups themselves comprise terminals of the chemical formula SO 2 NRQ + wherein Q, R are as defined above.
  • the fluorinated backbone may be an arbitrary linear polymer chain comprising, for example, repeating units of the chemical formula:
  • R F is selected from F, Cl, or —CF 3 , and is preferably selected as fluorine.
  • the element p of formula (II) above may be an integer between 0 and 16.
  • the element q may be an integer between 1 and 10, and the ratio p′/q′ may be between 0.5 and 16, p′ denoting an average value of all values of p in the repeating units and q′ denoting an average value of all values of q in the repeating units.
  • the fluoropolymer may comprise repeating units of the chemical formula:
  • terminals of chemical formula SO 2 NRQ + are covalently bonded to the backbone chain by groups of formula —[O—(CF 2 CF(R F )O) m —(CF 2 ) n ]—.
  • the element R′ F in formula (III) above may be selected from F, Cl, or —CF 3 , and is preferably selected as being fluorine or —CF 3 .
  • the element m may be an integer equal to 0 or 1
  • n may be an integer between 0 and 10.
  • R 1 is as R defined above
  • Q+ is as defined above
  • X ⁇ may be a anion selected from the group consisting of organic anions and lipophilic inorganic anions.
  • n is an integer between 0 and 10, preferably between 0 and 6.
  • n is 2.
  • n is an integer between 0 and 10, preferably between 2 and 6, more particularly between 2 and 4.
  • n is 2.
  • the fluoropolymer may be prepared by means of a method comprising-reacting a fluoropolymer comprising moieties having sulfonyl fluoride terminals with an amine, to obtain sulfonamide terminal groups.
  • This reaction is followed by reacting the product of the previous reaction with an alkylating agent to form an ion-exchanging quaternary ammonium group.
  • the amine can be written in the generic formula HNR 1 Q 1 where R 1 is as R defined above, and Q 1 is a group comprising a precursor of the tertiary amino group of the quaternary ammonium group Q + .
  • Copolymers comprising repeating units derived from fluoroolefin of the chemical formula CF 2 ⁇ CFR F , where R F is selected from F, Cl, and —CF 3 , as well as copolymers comprising repeating units derived from at least one functional monomer of chemical formula CF 2 ⁇ CF—O—(CF 2 CF(R′ F )O) m —(CF 2 ) n SO 2 F, where m is an integer equal to 0 or 1, n is an integer between 0 and 10, are compounds suitable for preparation of the fluoropolymer.
  • the fluoroolefin is preferably tetrafluoroethylene.
  • the group ensuring ion conduction in the polymer may have the chemical formula:
  • Y is a C 6 -C 10 aryl group, a heteroaryl group, or CR 7 R 8 where R 7 is hydrogen, a halogen atom, or a C 1 -C 20 alkyl group, or forms a closed chain with R 2 , R 5 , or R.
  • R 8 is hydrogen, a halogen atom, or a C 1 -C 20 alkyl group, or forms a closed chain with R 3 , R 6 , or R 7 .
  • Each chain formed by R 7 or R 8 contains from 2 to 10 carbon atoms and optionally 1 to 4 heteroatoms, and the heteroaryl group comprises from 5 to 10 atoms m the closed chain.
  • R 1 is hydrogen, a C 1 -C 20 alkyl group, or forms a closed chain R 2 or R 5 , the closed chain comprising between 2 and 10 carbon atoms and between 1 and 4 heteroatoms.
  • R 2 is a C 1 -C 20 alkyl group or forms a closed chain with R 1 , R 3 , R 5 , R 7 , or R 9 , the closed chain containing between 2 and 10 carbon atoms and between 1 and 4 heteroatoms such as nitrogen atoms.
  • R 3 is a C 1 -C 20 alkyl group or forms a closed chain with R 2 , R 6 , R 8 , or R 10 , the closed chain containing 2 to 10 carbon atoms and 1 to 4 heteroatoms.
  • R 4 is a C 1 -C 20 alkyl group.
  • R 5 is hydrogen, a halogen atom, or a C 1 -C 20 alkyl group, or form a closed chain with R 1 , R 2 , R 7 , or R 9 , the closed chain containing 2 to 10 carbon atoms and optionally 1 to 4 heteroatoms.
  • R 6 is hydrogen, a halogen atom, or a C 1 -C 20 alkyl group, or form a closed chain with R 3 , R 8 , or R 10 , the closed chain containing 2 to 10 carbon atoms and optionally 1 to 4 heteroatoms.
  • Each R 9 may be hydrogen, a halogen atom, a C 1 -C 20 alkyl group, or a closed chain with R 2 or R 5 , the closed chain containing 2 to 10 carbon atoms and optionally 1 to 4 heteroatoms.
  • Each R 10 may be hydrogen, a halogen atom, or a C 1 -C 20 alkyl group, or form a closed chain with R 3 or R 6 , the closed chain containing 2 to 10 carbon atoms and optionally 1-4 heteroatoms.
  • Z is an integer between 0 and 4, and the closed chain structures in the group of chemical formula (IV) illustrated above may be linked by bridges based on a C 1 -C 4 alkyl group.
  • amines suitable for preparation of the fluoropolymer are compounds having the chemical formula:
  • R 1 , R 2 , R 3 , R 5 , R 6 , R 9 , R 10 , Y and z are as defined above.
  • amines according to chemical formula (V) may be taken from the following families of compounds:
  • the amine is N,N,2,2-tetramethyl-1,3-propanediamine.
  • R 1 ⁇ H, R 2 ⁇ R 3 ⁇ CH 3 , R 5 ⁇ R 6 ⁇ R 9 ⁇ R 10 ⁇ H, z 1 and Y ⁇ CR 8 R 9 , with R 8 ⁇ R 9 ⁇ CH 3 .
  • the fluoropolymer of the membrane 8 of the composite electrode 1 also provides stability and resistance to the corrosive effect of the hydrogen peroxide present in a liquid electrolyte 3 of basic pH. It seems that resistance to the liquid electrolyte of basic pH is associated with resistance to hydrogen peroxide, particularly when hydrogen peroxide is present at a 5% mass concentration.
  • FIG. 4 illustrates a portion of a composite electrode according to this second embodiment, where the porous structure 7 further comprises molecules 39 of a fluoropolymer 9 , in order to improve the conduction of hydroxyl ions in the volume of the air electrode and render the porous structure 7 even more impermeable to any basic liquid electrolyte m contact with said porous structure.
  • the molecules 39 of fluoropolymer are an integral part of the porous structure 7 . They may, for example, be incorporated into the air electrode at the time of manufacture.
  • the porous structure 7 is typically obtained from a carbon powder comprising grains 6 which are joined by a binder during a step which may be a sintering step, for example.
  • the fluoropolymer 9 in polymerized form and suspended in the first liquid solution, can be mixed with the carbon powder during manufacture of the air electrode to ensure uniform distribution of the molecules 39 in the structure of the air electrode, as is schematically represented in FIG. 4 . Then a fluoropolymer 9 is deposited as a layer on this air electrode as described above.
  • this additional step is not represented, it is possible to further increase the ion conduction properties of the porous structure 7 , in both embodiments represented in FIGS. 3 and 4 .
  • a second liquid solution comprising an interpenetrating polymer or semi-interpenetrating polymer network.
  • the IPN or semi-IPN networks described in document FR0953021 can be deposited on the porous structure before formation of the membrane 8 . This second liquid solution and the IPN and semi-IPN networks are provided to penetrate the porous structure.
  • an evaporation step is carried out in order to evaporate the solvent of the second liquid solution and allow effective in-situ polymerization of the IPN or semi-IPN network in the porous structure 7 .
  • This IPN or semi-IPN network integrated with the porous structure 7 , allows better conduction of hydroxyl ions in the air electrode so as to deliver these ions throughout the volume of the porous structure.
  • a composite electrode 1 as described above has a service life about seven times greater than an air electrode according to the prior art, and in particular the air electrodes of a zinc-air battery using ambient air from which CO 2 has not been filtered.
  • the composite electrodes of the invention are resistant to the electrolytes of high alkalinity having hydroxyl ions in concentrations of about 8 mol/L or more encountered in metal-air batteries, particularly zinc-air batteries.
  • FIG. 5 shows a graph of the results of an experiment comparing the longevity of an air electrode according to the invention to the longevity of an air electrode according to the prior art.
  • the end of service life of electrodes of a battery is characterized by a loss of impermeability of the electrode to the electrolyte, which is indicated by the passage of liquid electrolyte through the electrode.
  • the difference between the two types of electrodes is even more pronounced in the right side of the graph of FIG. 5 .
  • the results to the right side of the graph represent the service life in hours of electrodes immersed in an electrolyte composed of an aqueous solution of KOH at a hydroxyl ion concentration of 8 mol/L saturated in ZnO.
  • the standard electrode without polymer remains impermeable for only 50 h.
  • an electrode according to the invention comprising a fluoropolymer as described above on its outer surface remains impermeable for 2900 h.
  • Synthesis of a polymer conductive to hydroxyl ions and impermeable to a liquid electrolyte of basic pH may in particular comprise the use of the following elements:
  • the compounds undergo an amidation reaction.
  • Aquivion®PFSA precursor 61 grams are placed in a flask containing 350 g hydrofluoroether.
  • the flask is equipped with a stirrer, a dropping funnel, a nitrogen gas inlet, and a gas outlet.
  • a stream of nitrogen is maintained throughout the process at a flow rate of about 1 liter per hour in order to keep the mixture anhydrous.
  • the polymer suspension is stirred at room temperature for about 2 hours.
  • the flask is then cooled to ⁇ 20′C using an external cold source and, while stirring the mixture, 60 grams of N,N,2,2-tetramethyl-1,3-propanediamine are slowly added for about 20 minutes through the dropping funnel.
  • the mixture is stirred at a temperature of ⁇ 20° C. for an additional 6 hours.
  • the polymer is then filtered, washed with 150 grams hydrofluoroether for one hour while stirring, and then treated twice with 200 grams of methanol for 1 hour while stirring. The whole is then treated twice with 200 grams of a solution comprising 5% KOH by mass while stirring for one hour. The polymer is then dried in a vacuum oven at 70° C. for 4 hours. 73 grams of dried polymer are thus obtained. Quantitation of the polymer indicates a concentration of 2.0 meq/g.
  • the polymer After cooling the mixture to room temperature, the polymer is filtered, washed with 250 ml acetonitrile for one hour while stirring, then washed three times with 250 ml methanol for 1 hour while stirring. The polymer is then dried in a vacuum oven at 70° C. for 4 hours. 73 grams of dried polymer are thus obtained.
  • Quantitation of the polymer indicates an iodide concentration of 0.85 meq/g.
  • Rf refers to the partially fluorinated backbone chain of Aquivion®PFSA, described above.
  • a first liquid solution of the fluoropolymer can then be obtained using the protocol described below.
  • This example describes how to obtain the first liquid solution used to manufacture a membrane 8 of the invention.
  • similar results can be obtained using other chemical compositions possessing the chemical properties described above to ensure both a good conduction of hydroxyl ions and an impermeability to a basic liquid electrolyte.
  • the impermeability and conduction properties of a membrane obtained from the compound synthesized according to the example described above have been characterized in different basic solutions.
  • a membrane 50 ⁇ m thick was prepared from the first liquid solution on a support specially provided for experimental purposes.
  • the membrane was treated with a KOH solution at a concentration of 1 mol/L, in a water ethanol mixture having a 1:1 mass ratio.
  • the membrane is then washed with water and placed in a flask containing a mixture as shown in the figure below, for the durations and at the temperatures indicated in the table below.
  • the membrane is placed for 24 hours in a solution containing 100 grams of sodium chloride at a concentration of 0.6 mol/L in a water-ethanol mixture having a 1:1 mass ratio, then washed with water.
  • the chloride content is measured and indicated in the table below.
  • the ion content of an untreated membrane, serving as a control sample, is 0.8 meq/g.
  • the ion contents indicated in this table reflect a stability in the impermeability and conduction properties of the prepared membrane over time, and good resistance in the presence of a strongly alkaline liquid.
  • the present invention may find applications in all metal-air batteries using a porous air electrode as a positive electrode.
  • the invention is of particular interest for protecting an air electrode in a zinc-air battery, offering good electrical performance with the general use of liquid electrolytes with a high concentration of hydroxyl ions.
US16/060,257 2015-12-11 2016-12-09 Composite air electrode and associated manufacturing method Abandoned US20180366737A1 (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09102322A (ja) * 1995-07-31 1997-04-15 Imura Zairyo Kaihatsu Kenkyusho:Kk 燃料電池用の固体高分子電解質膜およびその製造方法
US20030194599A1 (en) * 2002-04-16 2003-10-16 Sassa Robert L. Composite films for electrochemical devices
US20120058413A1 (en) * 2009-05-06 2012-03-08 Universite De Cergy Pontoise Interpenetrating network of anion-exchange polymers, production method thereof and use of same
WO2012098146A1 (fr) * 2011-01-21 2012-07-26 Solvay Specialty Polymers Italy S.P.A. Compositions liquides de polymères échangeurs d'anions fluorés

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR953021A (fr) 1947-08-29 1949-11-29 Gerard Dupont & Cie Ets Glacière à glace carbonique
US3553024A (en) * 1967-02-20 1971-01-05 Leesona Corp Electrochemical device utilizing an electrode comprising a continuous ptfe film which is gas permeable and free from liquid electrolyte seepage
CA968847A (en) * 1972-11-01 1975-06-03 William A. Armstrong Oxygen electrode
JPS57105970A (en) * 1980-12-23 1982-07-01 Toshiba Corp Air electrode
US4975172A (en) * 1987-03-02 1990-12-04 Westinghouse Electric Corp. Ionomeric polymers with ionomer membrane in pressure tolerant gas diffusion electrodes
US5242765A (en) * 1992-06-23 1993-09-07 Luz Electric Fuel Israel Limited Gas diffusion electrodes
GB0113989D0 (en) * 2001-06-08 2001-08-01 Eveready Battery Inc Separator for electrochemical cells
JP2007528843A (ja) * 2003-06-27 2007-10-18 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー フッ素化スルホンアミド化合物、およびそれらから製造された、電気化学電池に使用するためのポリマー電解質膜
US8227117B2 (en) * 2004-03-15 2012-07-24 Cabot Corporation Modified carbon products, their use in electrocatalysts and electrode layers and similar devices and methods relating to the same
DE102010062421A1 (de) * 2010-12-03 2012-06-06 Bayer Materialscience Aktiengesellschaft Sauerstoffverzehrelektrode und Verfahren zu ihrer Herstellung
JP5872813B2 (ja) * 2011-07-26 2016-03-01 ダイキン工業株式会社 含フッ素シルセスキオキサン重合体を用いた表面処理剤
CN102544520A (zh) * 2011-12-27 2012-07-04 上海尧豫实业有限公司 锌空电池气体扩散电极及其制备方法
EP2922127B1 (fr) * 2012-11-14 2017-11-29 Asahi Glass Company, Limited Procédé pour la fabrication de film de polymère ionique
US10249897B2 (en) 2013-09-25 2019-04-02 Lockheed Martin Energy, Llc Electrolyte balancing strategies for flow batteries
CN106660785B (zh) * 2013-11-01 2019-06-14 田纳西大学研究基金会 一种用于双电子、可逆氧气还原反应的催化剂
JP6070664B2 (ja) * 2014-09-19 2017-02-01 トヨタ自動車株式会社 空気電池

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09102322A (ja) * 1995-07-31 1997-04-15 Imura Zairyo Kaihatsu Kenkyusho:Kk 燃料電池用の固体高分子電解質膜およびその製造方法
US20030194599A1 (en) * 2002-04-16 2003-10-16 Sassa Robert L. Composite films for electrochemical devices
US20120058413A1 (en) * 2009-05-06 2012-03-08 Universite De Cergy Pontoise Interpenetrating network of anion-exchange polymers, production method thereof and use of same
WO2012098146A1 (fr) * 2011-01-21 2012-07-26 Solvay Specialty Polymers Italy S.P.A. Compositions liquides de polymères échangeurs d'anions fluorés

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US11189840B2 (en) 2021-11-30
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