EP2937449B1 - Gasdiffusionselektrode und herstellungsverfahren dafür - Google Patents

Gasdiffusionselektrode und herstellungsverfahren dafür Download PDF

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EP2937449B1
EP2937449B1 EP12891307.6A EP12891307A EP2937449B1 EP 2937449 B1 EP2937449 B1 EP 2937449B1 EP 12891307 A EP12891307 A EP 12891307A EP 2937449 B1 EP2937449 B1 EP 2937449B1
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gas diffusion
carbon black
diffusion electrode
layer
slurry
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EP2937449A4 (de
EP2937449A1 (de
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Feng Wang
Yinliang CAO
Jingjun Liu
Zhilin Li
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/34—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
    • C25B1/46—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis in diaphragm cells
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
    • C25B11/031—Porous electrodes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/042—Electrodes formed of a single material
    • C25B11/043—Carbon, e.g. diamond or graphene

Definitions

  • the present invention relates to the field of chemical engineering, particularly to a gas diffusion electrode suitable for the chlor-alkali industry and a preparation method thereof.
  • chlor-alkali industry plays an important role in promoting national economic development. Meanwhile, chlor-alkali industry is an industry with high energy consumption, so how to reduce the energy consumption of chlor-alkali industry to a minimum has always been an issue focused by many countries.
  • reaction equations of the traditional ion-exchange membrane brine electrolytic process with a hydrogen evolution electrode as the cathode are as follows: 2Cl - ⁇ Cl 2 +2e (1.36V) 2H 2 O+2e ⁇ 2OH - +H 2 (-0.83V) 2NaCl+2H 2 O ⁇ Cl 2 +2NaOH+H 2 (2.19V),
  • electrochemical reaction equations of the ion-exchange membrane brine electrolytic process with an oxygen diffusion electrode as the cathode are as follows: 2Cl - ⁇ Cl 2 +2e (1.36V) O 2 +2H 2 O+4e ⁇ 4OH - (0.4V) 2NaCl+H 2 O+1/2O 2 ⁇ Cl 2 +2NaOH (0.96V).
  • theoretic decomposition voltage thereof can be reduced by 1.23 V, the theoretic energy thereof can be saved up to 40%, and the electric energy saved will be 700KWh per ton of alkali, which make the process have very considerable application value.
  • Japanese Patent Publication 2007-327092 discloses a gas diffusion electrode having high resistance of water-pressure but low speed of deterioration, which is prepared using AB-6 carbon black as hydrophobic carbon black, AB-12 carbon black as hydrophilic carbon black, and Ag powder as a catalyst.
  • Japanese Patent Publication 2004-300451 discloses a gas diffusion electrode having stable performance, which is prepared with AB-6 carbon black as hydrophobic carbon black and Ag-plated metal web as a catalyst layer through the steps of dispersing the hydrophobic carbon black and an adhesive, filtering and drying, followed by hot-press molding the Ag-plated metal web, however such electrode is difficult to satisfy the requirement of large-scale industrial production of large electrode.
  • Cide CN101736360A discloses a gas diffusion electrode having a structure that a Ni web plated with Ag as a support is disposed between a gas diffusion layer and a catalyst layer, however such electrode involves problems such as low mechanical strength, being liable to form cracks on the surface of the electrode during the production thereof and difficult to release during the hot pressing process, and thus cannot satisfy the requirement of industrial production.
  • the present invention relates to a gas diffusion electrode comprising a current collector, a gas diffusion layer, a gas catalysis layer coated on the gas diffusion layer, and a liquid guide layer located on the gas catalysis layer; wherein the gas diffusion layer comprises highly-graphitized carbon black and polytetrafluoroethylene (PTFE), and the gas catalysis layer comprises a catalyst, acidified highly-graphitized carbon black and polytetrafluoroethylene; the highly-graphitized carbon black is the carbon black having a peak intensity ratio I D /I G between 0.3 and 1.0 in the Raman spectrum, and the degrees of graphitization in the gas diffusion layer and the gas catalysis layer may be the same or different; the current collector and the liquid guide layer are both silver-plated metal foam having a thickness of
  • the mass ratio of the highly-graphitized carbon black to polytetrafluoroethylene in the gas diffusion layer is (0.01-1): (0.01-0.1).
  • the mass ratio of the catalyst, the acidified highly-graphitized carbon black and polytetrafluoroethylene in the gas catalysis layer is (0.1-1): (0.1-1): (0.1-1).
  • the metal of the silver-plated metal foam is selected from nickel, titanium, tungsten, cobalt, or alloys thereof.
  • the catalyst in the gas catalysis layer is selected from silver powder or Ag/C composite catalyst; preferably, the catalyst has a particle size between 0.01 and 5 ⁇ m.
  • the diffusion electrode is applied as a gas diffusion electrode in chlor-alkali industry.
  • the gas diffusion layer is prepared from raw materials comprising highly-graphitized carbon black, water, Triton, polytetrafluoroethylene emulsion and isopropanol in a mass ratio of (0.01-1): (0.1-1): (0.01-0.1): (0.01-0.1): 1, wherein the aqueous isopropanol solution of Triton is used as a dispersion medium.
  • the gas catalysis layer is prepared from raw materials comprising a catalyst, acidified highly-graphitized carbon black, water, Triton, polytetrafluoroethylene solution and isopropanol in a mass ratio of (0.1-1): (0.1-1): (1-10): (0.1-1): (0.1-1) : 1, wherein the aqueous solution of Triton is used as a dispersion medium.
  • the preparation method of the gas diffusion layer comprises the following steps: (1) dispersing the highly-graphitized carbon black in the aqueous isopropanol solution comprising surfactant Triton, so as to obtain the slurry of the gas diffusion layer; dispersing this slurry by ultrasonic shear for 10 to 200 min; then adding 40 to 80 mass% of polytetrafluoroethylene emulsion, further dispersing by shear for 10 to 150 min; controlling the temperature during the dispersion of the gas diffusion layer slurry between 10 and 100°C, and the powder in the gas diffusion layer slurry having an average particle size between 0.2 and 10 ⁇ m after dispersion; setting the gas diffusion layer slurry for 5 to 100 h after dispersion; and controlling the solid content of the gas diffusion layer slurry between 5 and 40 wt%; and (2) coating the gas diffusion layer slurry evenly on the silver-plated metal foam of the current collector; after coating of the gas
  • the preparation method of the gas catalysis layer comprises the following steps: (1) dispersing the catalyst, the acidified graphitized carbon black in the aqueous isopropanol solution comprising surfactant Triton, so as to obtain the catalysis layer slurry; dispersing this slurry by ultrasonic shear for 10-200 min; then adding 40-80 mass% of polytetrafluoroethylene emulsion, further dispersing by shear for 10-150 min; and controlling the temperature during the dispersion of the catalysis layer slurry between 10-100°C and the powder in the catalysis layer slurry having an average particle size between 0.2-10 ⁇ m after dispersion; and (2) coating the catalysis layer slurry evenly on the gas diffusion layer of the assembly of the gas diffusion layer and the current collector; drying it at 40-120°C for 0.5-1 h after coating of the catalysis layer slurry; after the coating and drying of the catalysis layer
  • the silver-plated metal foam is prepared by plating Ag on the metal foam using electroplating, chemical plating, and replacement plating methods.
  • the catalyst used in the present invention includes Ag powder and Ag/C composite catalyst (the preparation thereof please refer to CN 101745390A ), and the Ag/C composite catalysts mentioned in the context are all those prepared according to patent publication CN 101745390A .
  • the present invention has the following advantageous effects.
  • a gas diffusion layer which has not only good electrical conductivity and gas permeability capability but also excellent resistance to water pressure, can be prepared by the processes of dispersing highly-graphitized carbon black in the aqueous isopropanol solution comprising a certain surfactant using ultrasonic shear and standing, so as to obtain a uniformly dispersed gas diffusion layer slurry; coating the gas diffusion layer slurry evenly on the silver-plated metal foam; and performing cold-pressing after drying the slurry.
  • a pre-molded gas diffusion electrode can be prepared by dispersing the catalyst and the acidified highly-graphitized carbon black in the aqueous isopropanol solution comprising a certain surfactant using ultrasonic shear so as to obtain a uniformly dispersed catalysis layer slurry; coating the catalysis layer slurry evenly on the gas diffusion layer; and performing cold-pressing after drying the slurry.
  • the catalysis layer obtained in this way not only has suitable hydrophilic and hydrophobic capacity which is beneficial to the gas-liquid-solid three-phase reaction, but also has anti-etching capacity and the capacity of preventing the occurrence of side reaction producing hydrogen peroxide, thus facilitating the long-term and stable operation of the electrode.
  • the pre-molded gas diffusion electrode is subjected to high-temperature baking in order to thoroughly remove the residual surfactant in the interior of the electrode, thereby facilitating the uniform of the pore structure during the hot-press molding process.
  • a gas diffusion electrode having a sandwich structure is formed by hot-pressing the silver-plated metal foam on the surface of the catalysis layer during the hot-pressing process, thus not only being beneficial to the progression of the three-phase reaction in the catalysis process, but also being capable of improving the electro-catalysis capacity of the electrode in a basic solution and the mechanical strength of the electrode itself due to the silver-plated metal foam. Therefore, the gas diffusion electrode provided by the present invention has good corrosion resistance and good electrical conductivity, and runs stably in a basic solution; thus it is suitable for the electrolysis reaction in chlor-alkali industry.
  • the highly-graphitized carbon black used in this example is prepared by graphitizing carbon black (Vulcan XC-72) in a high-temperature graphitization furnace at 2700°C for 6-10 h, and a Raman Spectrogram for measuring the graphitization degree thereof is shown in Figure 2 with I D /I G of 0.67.
  • the silver-plated nickel foam is prepared by electroplating, wherein the nickel foam is commercially available from Heze Tianyu Technical Developing Lt. Corp.
  • the acidified highly-graphitized carbon black is prepared by refluxing the graphitized carbon black in nitric acid solution (68 mass%) at 120°C for 6 to 10 h. Specifically,
  • the highly-graphitized carbon black used in this example is prepared by graphitizing carbon black (Vulcan XC-72) at 2600°C for 2-15 h, and has a Raman Spectrogram with I D /I G of 0.7-1.0.
  • the silver-plated nickel foam is prepared by electroplating, wherein the nickel foam is commercially available from Heze Tianyu Technical Developing Lt. Corp.
  • the acidified highly-graphitized carbon black is prepared by refluxing the graphitized carbon black in nitric acid solution (68 mass%) at 140°C for 6 to 10 h. Specifically,
  • the highly-graphitized carbon black used in this example is prepared by graphitizing carbon black (Vulcan XC-72) in a high-temperature graphitization furnace at 2900°C for 2-15 h, and has a Raman Spectrogram with I D /I G of 0.3-0.6.
  • the silver-plated nickel foam is prepared by electroplating, wherein the nickel foam is commercially available from Heze Tianyu Technical Developing Lt. Corp.
  • the acidified highly-graphitized carbon black is prepared by refluxing the graphitized carbon black in nitric acid solution (68 mass%) at 160°C for 6 to 10 h. Specifically,
  • the highly-graphitized carbon black used herein is prepared by graphitizing carbon black (Vulcan XC-72) in a high-temperature graphitization furnace at 2700°C for 6-10 h, and a Raman Spectrogram for measuring the graphitization degree thereof is shown in Figure 2 with I D /I G of 0.67.
  • the silver-plated nickel foam is prepared by electroplating, wherein the nickel foam is commercially available from Heze Tianyu Technical Developing Lt. Corp.
  • the acidified highly-graphitized carbon black is prepared by refluxing the graphitized carbon black in nitric acid solution (68 mass%) at 120°C for 6 to 10 h. Specifically,

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Inert Electrodes (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Claims (10)

  1. Gasdiffusionselektrode, umfassend einen Stromabnehmer, eine Gasdiffusionsschicht, eine auf der Gasdiffusionsschicht beschichtete Gaskatalyseschicht und eine auf der Gaskatalyseschicht befindliche flüssige Führungsschicht; wobei die Gasdiffusionsschicht hoch graphitierten Ruß und Polytetrafluorethylen umfasst und die Gaskatalyseschicht einen Katalysator, angesäuerten hoch graphitierten Ruß und Polytetrafluorethylen umfasst; der hoch graphitierte Ruß der Ruß mit einem Peak-Intensitätsverhältnis ID/IG zwischen 0,3 und 1,0 im Raman-Spektrum ist, und vorzugsweise wobei die Konzentration der sauerstoffhaltigen Funktionsgruppe auf der Oberfläche des angesäuerten graphitierten Rußes 0,5-2 mmol/g beträgt; die Graphitisierungsgrade in der Gasdiffusionsschicht und der Gaskatalyseschicht gleich oder verschieden sein können; der Stromabnehmer und die flüssige Führungsschicht beide versilberter Metallschaum mit einer Dicke von 0,1-20 µm sind und der versilberte Metallschaum davon gleich oder verschieden sein kann.
  2. Gasdiffusionselektrode nach Anspruch 1, wobei das Massenverhältnis des hoch graphitierten Rußes zu Polytetrafluorethylen in der Gasdiffusionsschicht (0,01-1) : (0,01-0,1) beträgt.
  3. Gasdiffusionselektrode nach Anspruch 1, wobei das Massenverhältnis des Katalysators, des angesäuerten hoch graphitierten Rußes und des Polytetrafluorethylens in der Gaskatalyseschicht (0,1-1): (0,1-1): (0,1-1) beträgt.
  4. Gasdiffusionselektrode nach einem der Ansprüche 1-3, wobei das Metall des versilberten Metallschaums ausgewählt ist aus Nickel, Titan, Wolfram, Cobalt und Legierungen davon.
  5. Gasdiffusionselektrode nach Anspruch 1, wobei der Katalysator in der Gaskatalyseschicht ausgewählt ist aus Silberpulver und Ag/C-Verbundkatalysator; vorzugsweise wobei der Katalysator eine Partikelgröße zwischen 0,01 und 5 µm aufweist.
  6. Gasdiffusionselektrode nach einem der Ansprüche 1-5, wobei die Diffusionselektrode eine in der Chlor-Alkali-Industrie angewandte Gasdiffusionselektrode ist.
  7. Verfahren zum Herstellen der Gasdiffusionselektrode nach Anspruch 6, wobei die Gasdiffusionsschicht aus Rohstoffen hergestellt wird, die Folgendes umfassen: hoch graphitierten Ruß, Wasser, Triton, Polytetrafluorethylenemulsion und Isopropanol in einem Massenverhältnis von (0,01-1): (0,1-1): (0,01-0.1): (0,01-0.1): 1, wobei die wässrige Isopropanollösung aus Triton als ein Dispersionsmittel verwendet wird.
  8. Verfahren zum Herstellen der Gasdiffusionselektrode nach Anspruch 6, wobei die Gaskatalyseschicht aus Rohstoffen hergestellt wird, die Folgendes umfassen: einen Katalysator, angesäuerten hoch graphitierten Ruß, Wasser, Triton, Polytetrafluorethylenlösung und Isopropanol in einem Massenverhältnis von (0,1-1) : (0,1-1) : (1-10) : (0,1-1): (0,1-1) : 1, wobei die wässrige Isopropanollösung aus Triton als ein Dispersionsmittel verwendet wird.
  9. Verfahren zum Herstellen der Gasdiffusionselektrode nach Anspruch 7, wobei das Herstellungsverfahren der Gasdiffusionsschicht die folgenden Schritte umfasst:
    (1) Dispergieren des hoch graphitierten Rußes in der wässrigen Isopropanollösung, umfassend Tensid Triton, um eine Aufschlämmung der Gasdiffusionsschicht zu erhalten; Dispergieren dieser Aufschlämmung durch Ultraschallscherung 10 bis 200 min lang; dann Hinzugeben von 40 bis 80 Ma.-% Polytetrafluorethylenemulsion, ferner Dispergieren durch Scherung 10 bis 150 min lang; Regeln der Temperatur während des Dispergierens der Gasdiffusionsschichtaufschlämmung zwischen 10 und 100 °C und wobei nach dem Dispergieren das Pulver in der Gasdiffusionsschichtaufschlämmung eine durchschnittliche Partikelgröße zwischen 0,2 und 10 µm aufweist; Einstellen der Gasdiffusionsschichtaufschlämmung 5 bis 100 h nach dem Dispergieren; und Steuern des Feststoffgehalts der Gasdiffusionsschichtaufschlämmung zwischen 5 und 40 Gew.-%; und
    (2) Beschichten der Gasdiffusionsschichtaufschlämmung gleichmäßig auf dem versilberten Metallschaum des Stromabnehmers; nach dem Beschichten der Gasdiffusionsschichtaufschlämmung, Trocknen dieser bei 40 bis 120 °C 5-10 h lang; nach dem Beschichten und Trocknen der Gasdiffusionsschichtaufschlämmung, Durchführen einer primären Kaltpressformbehandlung bei einem kalten Druck zwischen 0,1 und 2 MPa, einer Temperatur zwischen -10 und 50 °C und einer Verweilzeit zwischen 10 und 300 s, um eine Anordnung des Stromabnehmers und der Gasdiffusionsschicht zu erhalten.
  10. Verfahren zum Herstellen der Gasdiffusionselektrode nach Anspruch 8, wobei das Herstellungsverfahren der Gaskatalyseschicht die folgenden Schritte umfasst:
    (1) Dispergieren des Katalysators, des angesäuerten graphitierten Rußes in der wässrigen Isopropanollösung, umfassend Tensid Triton, um eine Katalyseschichtaufschlämmung zu erhalten; Dispergieren dieser Aufschlämmung durch Ultraschallscherung 10 bis 200 min lang; dann Hinzugeben von 40 bis 80 Ma.-% Polytetrafluorethylenemulsion, ferner Dispergieren durch Scherung 10-150 min lang; und Regeln der Temperatur während des Dispergierens der Katalyseschichtaufschlämmung auf 10-100 °C und wobei das Pulver in der Katalyseschichtaufschlämmung nach dem Dispergieren eine durchschnittliche Partikelgröße von 0,2-10 µm aufweist; und
    (2) Beschichten der Katalyseschichtaufschlämmung gleichmäßig auf der Gasdiffusionsschicht der Anordnung der Gasdiffusionsschicht und des Stromabnehmers; Trocknen bei 40-120 °C 0,5-1 h lang nach dem Beschichten der Katalyseschichtaufschlämmung; nach dem Beschichten und Trocknen der Katalyseschichtaufschlämmung, Durchführen einer sekundären Kaltpressformbehandlung der Anordnung bei einem kalten Druck zwischen 0,1 und 2 MPa bei einer Temperatur zwischen -10 und 50 °C und einer Verweilzeit zwischen 10 und 300 s, um eine vorgeformte Gasdiffusionselektrode zu erhalten; Brennen der vorgeformten Gasdiffusionselektrode bei hoher Temperatur zwischen 270 und 290 °C 1 bis 20 h lang; Anordnen des versilberten Metallschaums der flüssigen Führungsschicht auf der vorgeformten Gasdiffusionselektrode nach dem Brennen, und Durchführen eines Warmpressformens davon bei einem heißen Druck zwischen 2 und 12 MPa bei einer Warmpresstemperatur zwischen 330 und 450 °C und einer Verweilzeit zwischen 10 und 300 s, dadurch Erhalten der Gasdiffusionselektrode.
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EP2937449A4 (de) 2016-08-17
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