Electrode material by means of acetate precursor

Abstract

The present invention relates to metal oxides, their preparation from acetate salts, and their use as electrode material.

Description

[0001] Electrode material via acetate precursor

[0002] Description

[0003] The present invention relates to metal oxides, their production from acetate salts and their use as electrode material.

[0004] The catalytic production of hydrogen is a significant process in the chemical industry, gaining importance primarily due to the increasing demand for clean energy and the need to reduce greenhouse gas emissions. The main methods for catalytic hydrogen production are steam reforming of natural gas, partial oxidation, autothermal reforming, electrolysis, and photocatalytic water splitting. Currently, four main technologies are distinguished for the electrolysis of water to hydrogen: alkaline electrolysis (AEL), proton exchange membrane electrolysis (PMEL), high-temperature electrolysis (HTEL), and anion exchange membrane electrolysis (AEMEL).

[0005] The most commonly used electrolysis technology commercially is AEL. In this process, two metallic electrodes are immersed in an alkaline-aqueous, electrically conductive solution, the so-called electrolyte. Applying a direct current voltage then initiates the electrolytic splitting of the water, and hydrogen and hydroxide ions are produced as reaction products at the cathode (negatively charged).

[0006] Alkaline electrolysis is a proven technology with relatively low operating costs. Expensive precious metal catalysts are not required, as less expensive metal catalysts are sufficient. On the other hand, its efficiency is somewhat lower compared to alternative electrolysis processes. Currently, alkaline electrolysis is the preferred method for producing green hydrogen, where the electricity required for electrolysis comes from renewable energy sources. The catalytic effect of specific metal oxide compounds in the electrode material is described, for example, in the unpublished application EP 24186170.7.

[0007] Surprisingly, it was found that electrodes coated with the compounds according to the invention exhibit not only high electrochemical stability but also high mechanical stability, despite low electrical film resistance. Furthermore, it was found that the compounds according to the invention can be produced in situ in very high purity using an advantageous sol-gel process, without generating toxic or hazardous byproducts that would require complex separation and processing.

[0008] The object of the present invention is therefore to provide compounds that can be used advantageously in the production of high-quality electrode materials and can be produced with minimal effort (easy processing of the products, minimal occupational safety measures).

[0009] In a first aspect, the invention therefore relates to a compound of formula ABO3, AB2O4 or A2B2O6, wherein

[0010] A is selected from barium (Ba), strontium (Sr), lanthanum (La), praseodymium (Pr), and / or calcium (Ca), preferably lanthanum (La), barium (Ba) and / or strontium (Sr);

[0011] B is selected from iron (Fe), cobalt (Co), nickel (Ni), manganese (Mn), platinum (Pt), indium (Ir), ruthenium (Ru), palladium (Pd) and / or copper (Cu), preferably iron (Fe), cobalt (Co) and / or nickel (Ni), and

[0012] The compound exhibits at least one characteristic signal in a powder X-ray diffractogram (Cu-Ka radiation) 20±1 0at 22.0°, 22.2°, 23.1°, 24.4°, 25.5°, 31.5°, 32.6°, 32.7°, 33.0°, 32.7°, 37.1°, 39.1°, 39.7°, 40.5°, 41.2°, 43.2°, 43.9°, 45.5°, 46.1°, 46.9°, 47.2°, 47.5°, 50.6°, 51.6°, 56.2°, 57.9°, 58.1°, 58.4°, 66.2°, 68.5°, 69.0°, 92.1° and / or 96.6°. Characteristic signals within the meaning of the invention are, in each case, the most intense reflexes, in particular the most intense 20, more preferably the most intense 15, more preferably the most intense 10, and even more preferably the most intense 5 reflexes in an X-ray diffractogram.

[0013] Preferably, component A consists of different metal ions, in particular two different metal ions. More preferably, component A comprises a mixture of lanthanum (La) and strontium (Sr) ions or a mixture of barium (Ba) and strontium (Sr) ions. Even more preferably, component A consists of a mixture of lanthanum (La) and strontium (Sr) ions or a mixture of barium (Ba) and strontium (Sr) ions.

[0014] In the case of a La / Sr mixture, component A preferably comprises 40-70 mol% lanthanum and 30-60 mol% strontium, each based on the total component A. More preferably, component A consists of 40-70 mol% lanthanum and 30-60 mol% strontium.

[0015] In the case of a Ba / Sr mixture, this preferably comprises 40-70 mol% barium and 30-60 mol% strontium, each based on the total component A. More preferably, component A consists of 40-70 mol% barium and 30-60 mol% strontium.

[0016] Component B is selected from iron, cobalt, nickel, manganese, platinum, indium, ruthenium, palladium, and / or copper, preferably iron, cobalt, and / or nickel. Preferably, component B consists of different metal ions, particularly two different metal ions. More preferably, component B comprises a mixture of iron and cobalt ions or iron and nickel ions. Even more preferably, component B consists of a mixture of iron and cobalt ions or iron and nickel ions.

[0017] In the case of an Fe / Co mixture, component B preferably comprises 40-70 mol% iron and 30-60 mol% cobalt, each based on the total component B. More preferably, component B consists of 40-70 mol% iron and 30-60 mol% cobalt.

[0018] In the case of an Fe / Ni mixture, component B preferably comprises 40-70 mol% iron and 30-60 mol% nickel, each based on the total component B. More preferably, component B consists of 40-70 mol% iron and 30-60 mol% nickel.

[0019] The compound according to the invention preferably exists in a perovskite or spinel structure.

[0020] The compound according to the invention is particularly preferred in the following molecular formula: Bao.sSro.sCoo.sFeo.sOs, Lao,6Sro,4CoO3, Lao,6Sro,4FeO3, Lao,eSro,4NiO3, Lao.eSro^Nio.sFeo.sOs, Lao.eSro^Coo.sFeo.sOs, Bao.eSro^Nio.sFeo.sOs, or Bao,6Sro,4Coo,5Feo,s03.

[0021] The above-mentioned compounds according to the invention have at least one characteristic signal in the powder X-ray diffractogram (Cu-Ka radiation = 1.54 A) 20 ± 1°, preferably 20 ± 0.2° at 22.0°, 22.2°, 23.1°, 24.4°, 25.5°, 31.5°, 32.6°, 32.7°, 33.0°, 32.7°, 37.1°, 39.1°, 39.7°, 40.5°, 41.2°, 43.2°, 43.9°, 45.5°, 46.1°, 46.9°, 47.2°, 47.5°, 50.6°, 51.6°, 56.2°, 57.9°, 58.1°, 58.4°, 66.2°, 68.5°, 69.0°, 92.1° and / or 96.6°.

[0022] Preferably, the compound has the formula ABO3, wherein

[0023] A selected is lanthanum (La), barium (Ba) and / or strontium (Sr), in particular lanthanum (La) and strontium (Sr), or barium (Ba) and strontium (Sr);

[0024] B is selected as iron (Fe), cobalt (Co) and / or nickel (Ni), in particular iron (Fe) and cobalt (Co), or iron (Fe) and nickel (Ni), and the compound exhibits characteristic signals of 20 ± 1°, preferably 20 ± 0.2°, at 22.0°, 22.2°, 23.1°, 24.4°, 25.5°, 31.5°, 32.6°, 32.7°, 33.0°, 32.7°, 37.1°, 39.1°, 39.7°, 40.5°, 41.2°, 43.2°, 43.9°, 45.5°, 46.1°, 46.9°, 47.2°, 47.5° in a powder X-ray diffractogram (Cu-Ka radiation). 50.6°, 51.6°, 56.2°, 57.9°, 58.1°, 58.4°, 66.2°, 68.5°, 69.0°, 92.1 0 and / or has 96.6°. More preferably, the compound has the formula ABO3, wherein A is selected as lanthanum (La), barium (Ba) and / or strontium (Sr); in particular lanthanum (La) and strontium (Sr), or barium (Ba) and strontium (Sr);

[0025] B is selected as iron (Fe), cobalt (Co) and / or nickel (Ni), in particular iron (Fe) and cobalt (Co), or iron (Fe) and nickel (Ni), and the compound exhibits characteristic signals of 20±1°, preferably 20±0.2°, at 31.6° in a powder X-ray diffractogram (Cu-Ka radiation).

[0026] and optionally further characteristic signals 20±1°, preferably 20±0.2°, at 22.0°, 22.2°, 23.1°, 24.4°, 25.5°, 31.5°, 32.6°, 32.7°, 33.0°, 32.7°, 37.1°, 39.1°, 39.7°, 40.5°, 41.2°, 43.2°, 43.9°, 45.5°, 46.1°, 46.9°, 47.2°, 47.5°, 50.6°, 51.6°, 56.2°, 57.9°, 58.1°, 58.4°, 66.2°, 68.5°, 69.0°, exhibits 92.1° and / or 96.6°.

[0027] The compound is particularly favorably formulated as ABO3, whereby

[0028] A selected is lanthanum (La), and / or strontium (Sr);

[0029] especially lanthanum (La) and strontium (Sr);

[0030] B is selected as iron (Fe), cobalt (Co) and / or nickel (Ni), in particular iron (Fe) and cobalt (Co), or iron (Fe) and nickel (Ni), and the compound exhibits characteristic signals of 20±1°, preferably 20±0.2°, at 31.6°, 23.1°, 40.5°, 46.9°, 68.5° and 96.6° in a powder X-ray diffractogram (Cu-Ka radiation).

[0031] The compound is particularly favorably formulated as ABO3, whereby

[0032] A is selected, barium (Ba) and / or strontium (Sr);

[0033] especially barium (Ba) and strontium (Sr);

[0034] B is selected as iron (Fe), cobalt (Co) and / or nickel (Ni), in particular iron (Fe) and cobalt (Co), or iron (Fe) and nickel (Ni), and the compound exhibits characteristic signals of 20 ± 1°, preferably 20 ± 0.2°, at 31.6°, 22.0°, 45.5°, 56.2°, 66.2° and 92.1° in a powder X-ray diffractogram (Cu-Ka radiation). Preferably, Lao,6Sro,4Nio,5Feo,503 has the most intense signals of 20 ± 1°, more preferably 29 ± 0.2°, at 31.5°, 32.6°, and 57.9° in a powder X-ray diffractogram (Cu-Ka radiation).

[0035] and optionally further characteristic signals 20±1°, preferably 20±0.2°, at 23.1°, 25.5°, 37.1°, 40.5°, 43.9°, 46.9°, 68.5° and / or 96.6°.

[0036] Lao.eSro^Coo.sFeo.sOs preferably exhibited the most intense signals at 20±1°, more preferably at 20±0.2°, at 32.7°, 46.9° and 58.4° in a powder X-ray diffractogram (Cu-Ka radiation).

[0037] and optionally further characteristic signals 20±1°, preferably 20±0.2°, at 23.1°, 40.5°, 68.5° and / or 96.6°.

[0038] Bao.eSro^Coo.sFeo.sOs preferably exhibited the most intense signals at 20±1°, more preferably at 20±0.2°, at 31.5°, 45.5° and 56.2° in a powder X-ray diffractogram (Cu-Ka radiation).

[0039] and optionally further characteristic signals 20±1°, preferably 20±0.2°, at 22.2°, 31.6°, 39.1°, 51.6°, 66.2° and / or 92.1°.

[0040] Bao.eSro^Nio.sFeo.sOs preferably exhibited the most intense signals at 20±1°, more preferably at 20±0.2°, at 25.5°, 31.5° and 43.2° in a powder X-ray diffractogram (Cu-Ka radiation).

[0041] and optionally further characteristic signals 20±1°, preferably 20±0.2°, at 22.0°, 32.6°, 37.1°, 45.5°, 50.6°, 56.2°, 66.2° and / or 92.1°.

[0042] The compound according to the invention preferably has an electrical film resistance of 0.05 - 2 Q / cm. 2Measured according to DIN EN ISO 16773-1 on coated and uncoated metallic samples.

[0043] In another aspect, the invention relates to a method for producing the compound according to the invention, comprising the steps:

[0044] a) Mixing at least one acetate salt A'Ac and at least one acetate salt B'Ac with at least one (organic) solvent, preferably acetic acid, formamide, water, ethanol, isopropanol, or a mixture thereof;

[0045] b) Addition of at least one binder, preferably polyvinyl acetate, polyvinyl butyral or a mixture thereof;

[0046] c) Homogenize the mixture obtained after step b);

[0047] d) Thermal treatment of the homogenate obtained after step c) at temperatures up to 1000 °C;

[0048] e) Cooling the compound obtained after step d) to room temperature (20°C).

[0049] The preferred molar ratio of A'Ac to B'Ac is 0.5 - 1 ,5:0.5 - 3 in step a).

[0050] A' is preferably selected from the group consisting of Ba(ll), Sr(ll), La(lll), Pr(lll), and Ca(ll), preferably Ba(ll), La(lll) and Sr(ll).

[0051] B' is preferably selected from the group consisting of Fe(1 I, III), Co(1 I, III), Ni(11, III), Mn(11, III), Pt(11, III), lr(11, III), Ru(11, III), Pd(11, III) and Cu (I, II), preferably Fe(11, III), Co(11, III) and Ni (II, III).

[0052] Since the acetate anion (CHsCOO - ) is simply negatively charged, the following formulas result for A'Ac and B'Ac with a mono-, di- or trivalent metal (Me) cation: Me^CHsCOO), Me"(CH3COO)2 or Me in (CH3COO)3. The acetate salts also include their hydrates, solvates and polymorphs.

[0053] Preferably, A'Ac is selected from the group consisting of La(CH3COO)3 or a hydrate thereof, Sr(CH3COO)2 or a hydrate thereof, Ba(CH3COO)2 or a hydrate thereof and / or Ca(CH3COO)2 or a hydrate thereof.

[0054] Preferably, B'Ac is selected from the group consisting of Co(CH3COO)2 or a hydrate thereof, Fe(CH3COO)2 or a hydrate thereof, Ni(CH3COO)2 or a hydrate thereof, Mn(CH3COO)2 or a hydrate thereof, and / or Pt(CH3COO)2 or a hydrate thereof. In step a), the acetate salt A'Ac and B'Ac are preferably completely dissolved separately in water or organic solvent and the solutions are then mixed together.

[0055] A' and B' correspond to ions A and B respectively and may have a different oxidation state.

[0056] The binder is in particular a polymer soluble in the organic solvent or water, especially polyvinyl acetate, polyvinyl butyral or a mixture thereof.

[0057] The at least one binder can be added to the organic solvent or water before or after the respective salt has been dissolved in it, or after the acetate salts have been mixed.

[0058] After step a), a dispersion or a solution is preferably obtained.

[0059] After step b), the total mass of the binder is preferably present in a concentration of 1 - 10 wt.%, more preferably 1 - 3 wt.%, and even more preferably 0.05 - 3 wt.% based on the total amount of the mixture.

[0060] To generate the compound according to the invention, it is known to those skilled in the art that the acetate salts A'Ac and B'Ac must be used in the corresponding stoichiometric ratio. For example, Bao,5Sro,5Coo,5Feo,sO3 is produced with a mixture of the acetate salts Ba(CH3COO)2:Sr(CH3COO)2:Co(CH3COO)2:Fe(CH3COO)2 in the molar ratio 0.5:0.5:0.5:0.5.

[0061] In step c), the mixture obtained after step b) is homogenized. This can preferably be done by stirring, heating, shearing and / or in an ultrasonic bath.

[0062] After step c), a dispersion or a solution is preferably obtained. The process according to the invention is particularly preferably a sol-gel process in which a sol, i.e., a colloidal dispersion, is first formed from the solution by chemical reaction, from which larger particles subsequently emerge. The viscosity of the homogenate obtained after step c) is preferably 1–200 mPas, more preferably 50–150 mPas at 20°C, measured according to DIN 1342-2:2003-11. The pH value of the homogenate obtained after step c) is preferably 1–4.

[0063] Step d) involves the thermal treatment of the homogenate obtained after step c) at temperatures up to 1,000°C. Step d) may include the following substeps:

[0064] d1) Treating the homogenate obtained after step c) at 150 - 200 °C for preferably 60-300 s;

[0065] d2) Treating the mixture obtained after step d1) at 220 - 400 °C for preferably 60-600 s;

[0066] d3) Treating the mixture obtained after step d2) at 650 - 1000 °C for preferably 0.2 - 6 h, more preferably 1-6 h, and even more preferably 3-4 h.

[0067] The heating rate between steps d1) and d2) and / or between steps d2) and d3) is preferably 5 - 15 K / min.

[0068] The cooling rate between steps d) or d3) and e) is preferably 5-60 K / min, more preferably 5-15 K / min.

[0069] In the present process, no toxic or hazardous byproducts are formed during the thermal treatment in step d). The acetate salts react in this step to form the desired oxides, while harmless CO2 and water are formed as byproducts. In contrast, when other salts, such as nitrates, are used, toxic gases, such as nitrous gases, are released, which require complex removal processes. A further aspect of the present invention relates to a composition comprising at least one salt A'Ac (as described above), at least one salt B'Ac (as described above), at least one (organic) solvent (as described above), and at least one binder (as described above).

[0070] Preferably, a solid is obtained after step d3) or after step d). Preferably, the solvent is at least partially, and preferably completely, removed during step d).

[0071] Another aspect of the present invention is a compound obtainable according to the inventive method.

[0072] The compound according to the invention can be used as an electrode material.

[0073] In another aspect, the present invention relates to an electrode, preferably an anode, comprising a metallic substrate, carbon fleece and / or carbon paper and a compound according to the invention.

[0074] The metallic substrate is preferably in the form of a foil, plate, expanded metal or metal foam.

[0075] The metallic substrate, carbon fleece and / or carbon paper is preferably 10 pm to 2 mm thick, more preferably 100 pm to 800 pm, and even more preferably 200 pm to 5 mm thick.

[0076] Preferably the metallic substrate is selected from the group consisting of nickel, iron, copper and any alloys thereof, especially preferably nickel.

[0077] Preferably, the metallic substrate is coated with the compound according to the invention. The layer thickness of the compound on the metallic substrate is preferably 20 nm to 10 pm, more preferably 20–200 nm. A further aspect of the invention relates to the method for producing the electrode according to the invention. The method comprises the following steps:

[0078] a) Mixing at least one acetate salt A'Ac and at least one acetate salt B'Ac with at least one (organic) solvent, preferably acetic acid, formamide, water, isopropanol and / or ethanol;

[0079] ß) Addition of at least one binder, preferably polyvinyl acetate, polyvinyl butyral, or a mixture thereof;

[0080] y) Homogenizing the mixture obtained after step β);

[0081] b) Applying the homogenate obtained after step y) to a metallic substrate;

[0082] s) thermal treatment of the substrate obtained after step 6);

[0083] (|)) Cooling.

[0084] Steps a)-y) correspond to steps a)-c) of the process for producing the compound according to the invention. In step 6), the homogenate obtained after step y) is applied to a metallic substrate. The metallic substrate is as described above. Application is carried out by known methods, e.g., dipping, brushing, doctor blade application, or spraying.

[0085] The homogenate is preferably used in step 6) in an amount of 0.2 - 4 mg / cm². 2 , more preferably 0.8-2 mg / cm² 2 applied to the substrate.

[0086] Step s) preferably corresponds to step d) of the above-described process for producing the compound according to the invention. Step s) preferably comprises the following substeps:

[0087] s1) Treating the substrate obtained after step 6) at 150-200 °C preferably for 60-300 s;

[0088] s2) Treating the substrate obtained after step s1) at 220 - 400 °C for preferably 60 - 600 s; and

[0089] s3) Treating the substrate obtained after step s2) at 650 - 1000 °C for preferably 1 - 6 h. The cooling rate between steps s) or s3) and <|)) is preferably 5-60 K / min.

[0090] After step s) or s3), the (organic) solvent is at least partially, preferably completely, removed.

[0091] In another aspect, the invention relates to an electrode that can be obtained by the inventive method.

[0092] The electrode according to the invention can be used in an electrochemical cell. The electrochemical cell of the present invention comprises an electrode according to the invention, preferably an anode according to the invention, a cathode, an electrolyte, and optionally a membrane.

[0093] Figure 1 shows SEM images at different magnifications (A: 1 mm; B: 300 pm; C: 50 pm; D: Color-SEM via EDX, 20 pm; E: Color-SEM via EDX 20, 50 pm) of a nickel substrate (perforated sheet) coated with the compound Lao,6Sro,4Coo,5Feo,sO3 according to the invention.

[0094] Figure 2 shows powder X-ray diffractograms for the compounds Lao,6Sro,4Coo,5Feo,sO3, Lao.eSro^Nio.sFeo.sOs, Bao,6Sro,4Coo,5Feo,503, and Bao,6Sro,4Nio,5Feo,sO3.

[0095] The present invention is illustrated by the following example, but is not limited to it.

[0096] Example Lao,6Sro,4Coo,5Feo,s03, Lao,6Sro,4Nio,5Feo,s03, Bao,6Sro,4Coo,5Feo,s03 and Bao,6Sro,4Nio,5Feo,s03

[0097] 1. Weigh out metal acetates according to stoichiometry.

[0098] a) Lao,6Sro,4Coo,5Feo,s03

[0099]

[0100]

[0101] or b) Lao,6Sro,4Nio,5Feo,s03

[0102]

[0103] c) Bao,6Sro,4Coo,5Feo,s03

[0104]

[0105] or d) Bao,6Sro,4Nio,5Feo,s03

[0106]

[0107] 2. Dissolve in 7 ml of acetic acid (25%) at 80°C

[0108] 3. Ultrasonic bath for 5 minutes

[0109] 4. Addition of 400 pl of a saturated PVA solution made from 5 g PVA and 25 ml acetic acid (25%) at 80 °C

[0110] 5. Ultrasonic bath for 5 minutes

[0111] 6. Addition of 0.4 ml formamide

[0112] 7. Stir for 30 minutes at 80 °C

[0113] Coating / Heat treatment:

[0114] 8. Dip / spray coating of the substrate

[0115] 9. Dry on the hot plate at 180°C for 3 minutes

[0116] 10. Heat up to 360°C at 10 K / min, hold for 3 min

[0117] 11. Heat up to 700°C at 10 K / min, hold for 3 hours

[0118] 12. Cooling to room temperature at 10 K / min. The X-ray diffraction diffractograms of the compounds according to the invention are shown in Figure 2.

[0119] The present invention relates to the following points:

[0120] 1. Combination of the formula ABO3, AB2O4 or A2B2O6,

[0121] wherein A is selected from barium (Ba), strontium (Sr), lanthanum (La), praseodymium (Pr), and / or calcium (Ca), preferably lanthanum (La), barium (Ba) and / or strontium (Sr);

[0122] B is selected from iron (Fe), cobalt (Co), nickel (Ni), manganese (Mn), platinum (Pt), indium (Ir), ruthenium (Ru), palladium (Pd) and / or copper (Cu), preferably iron (Fe), cobalt (Co) and / or nickel (Ni), wherein the compound exhibits at least one characteristic signal of 20±1° in a powder X-ray diffractogram (Cu-Ka radiation) at 22.0°, 22.2°, 23.1°, 24.4°, 25.5°, 31.5°, 32.6°, 32.7°, 33.0°, 32.7°, 37.1°, 39.1°, 39.7°, 40.5°, 41.2°, 43.2°, 43.9°, 45.5°, 46.1°, 46.9°, 47.2°, 47.5°, 50.6°, 51.6°, 56.2°, 57.9°, 58.1°, 58.4°, 66.2°, 68.5°, 69.0°, 92.1° and / or 96.6°.

[0123] 2. Connection according to point 1, where A

[0124] • La and Sr; or

[0125] • Includes Ba and Sr; and / or

[0126] B

[0127] • Fe and Co; or

[0128] • Fe and Ni

[0129] includes.

[0130] 3. Connection according to point 2, where A

[0131] • 40–70 mol% La and 30–60 mol% Sr, each based on A; or • 40–70 mol% Ba and 30–60 mol% Sr, each based on A; and / or

[0132] B• 40 - 70 mol-% Fe and 30 - 60 mol-% Co each based on B; or

[0133] • Includes 40 - 70 mol-% Fe and 30 - 60 mol-% Ni, each based on B.

[0134] . Compound according to one of points 1-3, where the compound is in a perovskite structure or a spinel structure.

[0135] . Connection to one of points 1-4, where the connection is Bao.sSro.sCoo.sFeo.sOs, Lao,6Sro,4Co03, Lao,6Sro,4Fe03, Lao,6Sro,4Ni03, Lao,6Sro,4Nio,5Feo,s03, Lao.eSro^Coo.sFeo.sOs, Bao,6Sro,4Nio,5Feo,503 or Bao,6Sro,4Coo,5Feo,s03.

[0136] . Connection according to one of points 1-5, where the connection has an electrical layer resistance of 0.05 - 2 Q / cm 2, measured according to DIN EN ISO 16773-1 on coated and uncoated metallic samples, exhibits.

[0137] . Method for producing a compound according to any one of points 1-6, comprising the steps:

[0138] a) Mixing at least one acetate salt A'Ac and at least one acetate salt B'Ac with at least one (organic) solvent, preferably acetic acid, formamide, water, ethanol, isopropanol, or a mixture thereof;

[0139] b) Addition of at least one binder, preferably polyvinyl acetate, polyvinyl butyral or a mixture thereof;

[0140] c) Homogenize the mixture obtained after step b);

[0141] d) Thermal treatment of the homogenate obtained after step c) at temperatures up to 1000 °C;

[0142] e) Cooling the substance obtained after step d) to room temperature.

[0143] . Method according to point 7, wherein the molar ratio of A'Ac : B'Ac in step a) is 0.5-1.5:0.5-3. 9. Method according to point 7 or 8, wherein the mixture after step a) is a solution or dispersion.

[0144] 10. Method according to one of points 7-9, wherein A' is selected from the group consisting of Ba(ll), Sr(ll), La(lll), Pr(lll), and Ca(ll), preferably Ba(ll), La(lll) and Sr(ll), and B' is selected from the group consisting of Fe(ll, III), Co(ll, III), Ni(ll, III), Mn(ll, III), Pt(ll, III), lr(ll, III), Ru(ll, III), Pd(ll, III) and Cu (I, II), preferably Fe(ll, III), Co(ll, III) and Ni (II, III).

[0145] 11. Method according to one of points 7-10, wherein A'Ac is selected from the group consisting of La(CH3COO)3 or a hydrate thereof, Sr(CH3COO)2 or a hydrate thereof, Ba(CH3COO)2 or a hydrate thereof and / or Ca(CH3COO)2 or a hydrate thereof.

[0146] 12. Method according to one of points 7-11, wherein B'Ac is selected from the group consisting of Co(CH3COO)2 or a hydrate thereof, Fe(CH3COO)2 or a hydrate thereof, Ni(CH3COO)2 or a hydrate thereof, Mn(CH3COO)2 or a hydrate thereof and / or Pt(CH3COO)2 or a hydrate thereof.

[0147] 13. Method according to any of points 7-12, wherein the binder is polyvinyl acetate, polyvinyl butyral or a mixture thereof.

[0148] 14. Method according to one of points 7-13, wherein the binder according to step b) is present in a concentration of 1 - 10 wt.%, preferably 1 - 3 wt.%, more preferably 0.05 - 3 wt.% based on the total amount.

[0149] 15. Method according to one of points 7-14, wherein homogenization in step c) is carried out by ultrasound, shearing, heat input and / or stirring.

[0150] 16. Method according to any one of points 7-15, wherein a dispersion or solution is obtained after step c). 17. Method according to any one of points 7-16, wherein the viscosity of the homogenate obtained after step c) is 1-200 mPas at 20°C, measured according to DIN 1342-2:2003-11: Viscosity for Newtonian fluids

[0151] 18. Method according to one of points 7-17, wherein the pH of the homogenate is between 1-4.

[0152] 19. Procedure according to one of points 7-18, where step d) comprises the following steps:

[0153] d1) Treating the homogenate obtained after step c) at 150 - 200 °C for preferably 60 - 300 s;

[0154] d2) Treating the mixture obtained after step d1) at 220–400 °C for preferably 60–600 s; and

[0155] d3) Treating the mixture obtained after step d2) at 650 - 1000 °C for preferably 0.2 - 6 h, more preferably 1 - 6 h, and even more preferably 3 - 4 h.

[0156] 20. Method according to one of points 7-19, wherein the heating rate between steps d1) and d2) and / or between steps d2) and d3) is 5 - 15 K / min.

[0157] 21. Method according to one of points 7-20, wherein the cooling rate between steps d) or d3) and e) is 5 - 60 K / min, preferably 5 - 15 K / min.

[0158] 22. Composition comprising at least one salt A'Ac, at least one salt B'Ac, at least one organic solvent and at least one binder.

[0159] 23. Use of the connection according to one of points 1-6 as

[0160] Electrode material.24. Electrode, preferably anode, comprising a metallic substrate, carbon fleece and / or carbon paper and a compound according to any one of points 1-6.

[0161] 25. Electrode according to point 24, wherein the metallic substrate is a foil, plate, expanded metal or metal foam, preferably with a thickness of 10 pm - 2 mm, more preferably 100 pm - 800 pm, more preferably 200 pm - 5 mm.

[0162] 26. Electrode according to point 24 or 25, wherein the metallic substrate is selected from the group consisting of nickel, iron, copper and any alloys thereof, preferably nickel.

[0163] 27. Electrode according to one of points 24-26, wherein the metallic substrate is coated with the compound according to one of points 1-6.

[0164] 28. Electrode according to one of points 24-27, wherein the coating has a thickness of 20 nm - 10 pm, preferably 20 - 200 nm.

[0165] 29. Method for producing an electrode according to one of points 24-28 comprising the steps:

[0166] a) Mixing at least one acetate salt A'Ac and at least one acetate salt B'Ac with at least one (organic) solvent, preferably acetic acid, formamide, water, isopropanol and / or ethanol; β) Adding a binder, preferably polyvinyl acetate, polyvinyl butyral or a mixture thereof;

[0167] y) Homogenizing the mixture obtained after step β);

[0168] b) Applying the homogenate obtained after step y) to a metallic substrate;

[0169] s) thermal treatment of the substrate obtained after step 6);

[0170] (|)) Cooling.

[0171] 30. Method according to point 29, wherein homogenization in step y) is carried out by ultrasound, shearing, heat application or stirring. 31. Method according to point 29 or 30, wherein a dispersion or solution is present after step y).

[0172] 32. Method according to one of points 29-31, wherein in step 6) the homogenate is added in an amount of 0.2-4 mg / cm² 2 preferably 0.8-2 mg / cm² 2 , is applied to the substrate.

[0173] 33. Procedure according to one of points 29-32, where step s) comprises the following steps:

[0174] s1) Treat the substrate obtained after step o) at 150-200 °C for 60-300 s;

[0175] s2) Treating the substrate obtained after step s1) at 220–400 °C for preferably 60–600 s; and

[0176] s3) Treating the substrate obtained after step s2) at 650 - 1000 °C for preferably 1 - 6 h.

[0177] 34. Method according to one of points 29-33, wherein the cooling rate between steps s) or s3) and <t>) 5 - 60 K / min is.

[0178] 35. Electrode obtainable by a process according to one of points 29-34.

[0179] 36. Use of the electrode according to one of points 24-28 or 35 in an electrochemical cell.

[0180] 37. Electrochemical cell comprising an electrode, preferably an anode according to one of points 24-28 or 35, a cathode, an electrolyte and optionally a membrane.< / t>

Claims

Claims 1. Combination of the formula ABO3, AB2O4 or A2B2O6, wherein A is selected from barium (Ba), strontium (Sr), lanthanum (La), praseodymium (Pr), and / or calcium (Ca), preferably lanthanum (La), barium (Ba) and / or strontium (Sr); B is selected from iron (Fe), cobalt (Co), nickel (Ni), manganese (Mn), platinum (Pt), indium (Ir), ruthenium (Ru), palladium (Pd) and / or copper (Cu), preferably iron (Fe), cobalt (Co) and / or nickel (Ni), and wherein the compound exhibits at least one characteristic signal of 20±1° in a powder X-ray diffractogram (Cu-Ka radiation) at 22.0°, 22.2°, 23.1°, 24.4°, 25.5°, 31.5°, 32.6°, 32.7°, 33.0°, 32.7°, 37.1°, 39.1°, 39.7°, 40.5°, 41.2°, 43.2°, 43.9°, 45.5°, 46.1°, 46.9°, 47.2°, 47.5°, 50.6°, 51.6°, 56.2°, 57.9°, 58.1°, 58.4°, 66.2°, 68.5°, 69.0°, 92.1° and / or 96.6°.

2. Compound according to claim 1, wherein A • La and Sr; or • Includes Ba and Sr; and / or B • Fe and Co; or • Fe and Ni includes and / or wherein A • 40–70 mol% La and 30–60 mol% Sr, each based on A; or • 40–70 mol% Ba and 30–60 mol% Sr, each based on A; and / or B • 40-70 mol% Fe and 30-60 mol% Co, each based on B; or • 40-70 mol% Fe and 30-60 mol% Ni, each based on B, comprise and / or wherein the compound is in a perovskite structure or a spinel structure and the compound is in particular Bao.sSro.sCoo.sFeo.sOs, Lao,eSro,4CoO3, Lao,6Sro,4FeO3, Lao,6Sro,4NiO3, Lao.eSro^Nio.sFeo.sOs, Lao,6Sro,4Coo,5Feo,s03, Bao,6Sro,4Nio,5Feo,503 or Bao,6Sro,4Coo,5Feo,503.

3. A method for producing a compound according to claim 1 or 2, comprising the steps of: (a) Mixing at least one acetate salt A'Ac and at least one acetate salt B'Ac with at least one (organic) solvent, preferably acetic acid, formamide, water, ethanol, isopropanol, or a mixture thereof; (b) Addition of at least one binder, preferably polyvinyl acetate, polyvinyl butyral or a mixture thereof; (c) Homogenize the mixture obtained after step b); (d) Thermal treatment of the homogenate obtained after step c) at temperatures up to 1000 °C; (e) Cooling the substance obtained after step d) to room temperature.

4. The method of claim 3, wherein A' is selected from the group consisting of Ba(ll), Sr(ll), La(lll), Pr(lll), and Ca(ll), preferably Ba(ll), La(lll) and Sr(ll), and / or B' is selected from the group consisting of Fe(ll, III), Co(ll, III), Ni(ll, III), Mn(ll, III), Pt(ll, III), lr(ll, III), Ru(ll, III), Pd(ll, III) and Cu(I, II), preferably Fe(ll, III), Co(ll, III) and Ni(II, III) and / or wherein A'Ac is selected from the group consisting of La(CH3COO)3 or a hydrate thereof, Sr(CH3COO)2 or a hydrate thereof, Ba(CH3COO)2 or a hydrate thereof and / or Ca(CH3COO)2 or a hydrate thereof and / or wherein B'Ac is selected from the group consisting of Co(CH3COO)2 or a hydrate thereof, Fe(CH3COO)2 or a hydrate thereof, Ni(CH3COO)2 or a hydrate thereof, Mn(CH3COO)2 or a hydrate thereof and / or Pt(CH3COO)2 or a hydrate thereof.

5. Method according to any one of claims 3-4, wherein the binder is polyvinyl acetate, polyvinyl butyral or a mixture thereof and is preferably, according to step b), present in a concentration of 1-10 wt.%, preferably 1-3 wt.%, more preferably 0.05-3 wt.% based on the total amount.

6. A method according to any one of claims 3-5, wherein step d) comprises the following steps: d1) Treating the homogenate obtained after step c) at 150 - 200 °C for preferably 60 - 300 s; d2) Treating the mixture obtained after step d1) at 220 - 400 °C for preferably 60 - 600 s; d3) Treating the mixture obtained after step d2) at 650 - 1000 °C for preferably 0.2 - 6 h, more preferably 1 - 6 h, even more preferably 3 - 4 h and / or wherein The heating rate between steps d1) and d2) and / or between steps d2) and d3) is 5 - 15 K / min and / or where The cooling rate between steps d) or d3) and e) is 5 - 60 K / min, preferably 5 - 15 K / min.

7. Composition comprising at least one salt A'Ac, at least one salt B'Ac, at least one organic solvent and at least one binder.

8. Use of the compound according to one of claims 1-2 as electrode material.

9. Electrode, preferably anode, comprising a metallic substrate, carbon fleece and / or carbon paper, and a compound according to any one of claims 1-2, wherein the metallic substrate is preferably a foil, plate, expanded metal, or metal foam, and / or wherein the metallic substrate, carbon fleece, and / or carbon paper preferably has a thickness of 10 pm to 2 mm, more preferably 100 pm to 800 pm, and even more preferably 200 pm to 5 mm.

10. Electrode according to claim 9, wherein the metallic substrate is selected from the group consisting of nickel, iron, copper, and any alloys thereof, preferably nickel and / or wherein the metallic substrate is coated with the compound according to one of claims 1-2 and / or wherein The coating has a thickness of 20 nm - 10 pm, preferably 20 - 200 nm.

11. Method for producing an electrode according to one of claims 9-10 comprising the steps: a) Mixing at least one acetate salt A'Ac and at least one acetate salt B'Ac with at least one (organic) solvent, preferably acetic acid, formamide, water, isopropanol and / or ethanol; β) Adding a binder, preferably polyvinyl acetate, polyvinyl butyral or a mixture thereof; y) Homogenizing the mixture obtained after step β), preferably by ultrasound, shearing, heat input or stirring; ö) Applying the homogenate obtained after step y) to a metallic substrate; s) thermal treatment of the substrate obtained after step o); <D) Abkühlen.

12. The method of claim 11, wherein after step y) a dispersion or solution is present and / or wherein in step o) the homogenate is added in an amount of 0.2-4 mg / cm² 2 preferably 0.8-2 mg / cm² 2 , is applied to the substrate and / or wherein Step s) includes the following steps: s1) Treating the substrate obtained after step o) at 150–200 °C for 60–300 s; s2) Treating the substrate obtained after step s1) at 220–400 °C for preferably 60–600 s; and s3) Treating the substrate obtained after step s2) at 650 - 1000 °C for preferably 1 - 6 h and / or wherein the cooling rate between steps s) or s3) and <t>) 5 - 60 K / min is.

13. Electrode obtainable by a method according to one of claims 11-12.

14. Use of the electrode according to one of claims 9-10 or 13 in an electrochemical cell.

15. Electrochemical cell comprising an electrode, preferably anode, according to one of claims 9-10 or 13, a cathode, an electrolyte and optionally a membrane.< / t>

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