EP0059902B1 - Aus Nickelpulver heissgepresste hochporöse Elektrode für alkalische Wasserelektrolyseure - Google Patents

Aus Nickelpulver heissgepresste hochporöse Elektrode für alkalische Wasserelektrolyseure Download PDF

Info

Publication number
EP0059902B1
EP0059902B1 EP82101509A EP82101509A EP0059902B1 EP 0059902 B1 EP0059902 B1 EP 0059902B1 EP 82101509 A EP82101509 A EP 82101509A EP 82101509 A EP82101509 A EP 82101509A EP 0059902 B1 EP0059902 B1 EP 0059902B1
Authority
EP
European Patent Office
Prior art keywords
electrode
nickel
nickel powder
solution
sintered
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP82101509A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0059902A1 (de
Inventor
Henning Prof. Dr. Ewe
Eduard W. Prof. Dr. Justi
Peter Dr. Brennecke
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Schnapka Herbert Dr
Original Assignee
Schnapka Herbert Dr
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Schnapka Herbert Dr filed Critical Schnapka Herbert Dr
Priority to AT82101509T priority Critical patent/ATE14323T1/de
Publication of EP0059902A1 publication Critical patent/EP0059902A1/de
Application granted granted Critical
Publication of EP0059902B1 publication Critical patent/EP0059902B1/de
Expired legal-status Critical Current

Links

Images

Classifications

    • 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
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound

Definitions

  • the invention relates to a highly porous electrode hot-pressed from nickel powder for alkaline water electrolysers, in particular an electrode which is covered on its inner and outer surface with a 0.0025-0.1 ⁇ m thick oxide layer, and to processes for its production.
  • a high corrosion resistance in strongly alkaline electrolytes is achieved due to the layer consisting almost entirely of nickel oxide.
  • the nickel support structure is protected in particular by the nickel oxide layer against oxidation to form voluminous oxides or hydroxides. This significantly extends the service life of the electrode.
  • the O 2 deposition is catalyzed by this nickel oxide layer (DE-OS 29 03 407).
  • the object of the invention is to provide an electrode of the type mentioned at the outset, which has an improved (“doctoralized •) catalytic effect and in which the H 2 and O 2 deposition take place even at high current densities with low polarizations.
  • the long-term stability should be increased by reducing the oxidation of the nickel of the electrode body, since the oxidation continues slowly even when the surface is essentially made of nickel oxide.
  • the surface layer consists of a nickel-titanium mixed oxide.
  • a method for producing the electrode is characterized in that the electrode is hot pressed or sintered from a nickel powder at 300-500 ° C, which is alloyed with 1-15 wt .-%, preferably about 2 wt .-% titanium and the surface layer is generated from a nickel-titanium mixed oxide by oxidation of the electrode surface.
  • a NiTi x (OH) 2 layer can be applied chemically, preferably electrochemically, to the surface of the electrode and the nickel-titanium mixed oxide layer can be produced from it by thermal decomposition at temperatures above 150 ° C .
  • Another method for producing the electrode is characterized in that before or after the hot pressing or sintering, titanium is applied to the nickel surface in the form of an aqueous titanyl sulfate solution (TiO (SO 4 ) solution), which is then dried, the solution being used for the solution such an amount and / or concentration is selected that after hot pressing or sintering the highly porous electrode at 300-500 ° C or after annealing the hot-pressed or sintered highly porous electrode at 150-500 ° C in air or in a 0 2 atmosphere Titanium content in the surface surface nickel-titanium mixed oxide layer is about 2-3 wt .-%.
  • the solution can be mixed with the nickel powder before pressing.
  • the electrode pre-pressed from nickel powder at room temperature is impregnated with the solution and then hot pressed or sintered.
  • the electrode, hot-pressed or sintered from nickel powder can be soaked and tempered with the solution.
  • the nickel-titanium mixed oxide layer covering the inner and outer surface of the electrode can be achieved by tempering the nickel electrodes in air or in a 0 2 atmosphere.
  • the temperature should be at least 150 ° C and at most 500 ° C.
  • the amount of 0 2 required for the oxidation can also be provided by using nickel powder for the production of the electrode which has an air and / or oxygen loading sufficient for the nickel-titanium mixed oxide layer when the electrode is hot pressed or sintered to train, which are carried out at temperatures between 300 and 500 ° C.
  • the catalytically and stabilizing mixed oxide layer is already achieved by hot pressing or sintering in air, thus saving a subsequent work step.
  • the annealing time should be a minimum of 0.5 h.
  • the tempering time can be extended up to 20 h.
  • the catalytically and stabilizing nickel-titanium mixed oxide layer must have a minimum thickness in the range of 0.002 5-0.1 wm, which in any case ensures a tight, closed covering of the nickel supporting structure of the electrode.
  • the electrode according to the invention resists the strongest known oxidant even in long-term operation. namely oxygen in statu nascendi and is therefore superior to platinum, which cannot be used for electrodes for water electrolysis for economic reasons.
  • electrodes according to the invention are particularly well suited for use in newer electrolyzers. They can be used both as anodes and as cathodes.
  • the impregnated carbonyl nickel powder After the impregnated carbonyl nickel powder has dried, it is mixed with 4 g of salt filler (Na 2 C0 3 ; grain size 50-75 ⁇ m) to achieve the necessary macro- or volume porosity, smoothly coated into a die of 40 mm inside diameter, with 0.32 to / cm 2 cold pressed and after heating in air at 400 ° C with 0.8 to / cm 2 hot pressed to a disc-shaped electrode. After the pressing process, the added salt filler is dissolved out in hot distilled water.
  • salt filler Na 2 C0 3 ; grain size 50-75 ⁇ m
  • carbonyl nickel powder carbonyl nickel T 255; grain fraction ⁇ 50 ⁇ m
  • 4 g salt filler Na 2 C0 3 ; grain fraction 50-75 ⁇ m
  • the added salt filler is dissolved out in hot water and the electrode is dried.
  • the porous Ni electrode is mixed with an aqueous titanyl sulfate solution containing 0.24 g of Ti, dried and annealed at 200 ° C. for 4 hours to form the Ni-Ti mixed oxides.
  • An electrode to be used as an anode is produced as in the first exemplary embodiment, but the hot pressing is carried out in a gas-tight steel mold without any appreciable air access. After the salt filler has been removed, the electrode is dried and heated in air at 200 ° C. for 10 hours. By hot-pressing the electrode in the absence of air, a stronger welding of the Ni grains is achieved.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Powder Metallurgy (AREA)
  • Inert Electrodes (AREA)
EP82101509A 1981-03-11 1982-02-27 Aus Nickelpulver heissgepresste hochporöse Elektrode für alkalische Wasserelektrolyseure Expired EP0059902B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT82101509T ATE14323T1 (de) 1981-03-11 1982-02-27 Aus nickelpulver heissgepresste hochporoese elektrode fuer alkalische wasserelektrolyseure.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3109183 1981-03-11
DE3109183A DE3109183C2 (de) 1981-03-11 1981-03-11 Aus Nickelpulver heißgepreßte hochporöse Elektrode für alkalische Wasserelektrolyseure

Publications (2)

Publication Number Publication Date
EP0059902A1 EP0059902A1 (de) 1982-09-15
EP0059902B1 true EP0059902B1 (de) 1985-07-17

Family

ID=6126884

Family Applications (1)

Application Number Title Priority Date Filing Date
EP82101509A Expired EP0059902B1 (de) 1981-03-11 1982-02-27 Aus Nickelpulver heissgepresste hochporöse Elektrode für alkalische Wasserelektrolyseure

Country Status (13)

Country Link
US (1) US4447302A (cs)
EP (1) EP0059902B1 (cs)
JP (1) JPS57161078A (cs)
AR (1) AR228643A1 (cs)
AT (1) ATE14323T1 (cs)
AU (1) AU547889B2 (cs)
BR (1) BR8201247A (cs)
CA (1) CA1191815A (cs)
CS (1) CS241504B2 (cs)
DD (1) DD201701A5 (cs)
DE (1) DE3109183C2 (cs)
ES (1) ES510290A0 (cs)
HU (1) HU188056B (cs)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3318758C2 (de) * 1983-05-24 1985-06-13 Kernforschungsanlage Jülich GmbH, 5170 Jülich Diaphragma auf Nickeloxidbasis und Verfahren zur Herstellung desselben
US4648945A (en) * 1985-03-21 1987-03-10 Westinghouse Electric Corp. Bipolar plating of metal contacts onto oxide interconnection for solid oxide electrochemical cell
JPS6286187A (ja) * 1985-10-09 1987-04-20 Asahi Chem Ind Co Ltd 水素発生用の電極
KR20020074451A (ko) * 1999-11-18 2002-09-30 프로톤 에너지 시스템즈, 인코포레이티드 높은 압력 차이 전기화학 전지
DE10007480A1 (de) * 2000-02-18 2001-08-23 Provera Ges Fuer Projektierung Bipolare Elektrode mit Halbleiterbeschichtung und damit verbundenes Verfahren zur elektrolytischen Wasserspaltung
WO2004015805A2 (en) * 2002-08-09 2004-02-19 Proton Energy Systems, Inc. Electrochemical cell support structure
KR100930790B1 (ko) * 2009-02-18 2009-12-09 황부성 수소산소 발생용 전극판 및 그를 제조하기 위한 제조방법
US20150287980A1 (en) * 2012-10-12 2015-10-08 Zhongwei Chen Method of producing porous electrodes for batteries and fuel cells

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE290407C (cs) *
DE1269213B (de) * 1963-09-27 1968-05-30 Asea Ab Verfahren zur Herstellung von poroesen Brennstoffelektroden fuer Brennstoffelemente
US3505118A (en) * 1966-12-05 1970-04-07 Du Pont Fuel cell and process for producing electric current using titanium dioxide catalyst
FR2163638A1 (cs) * 1971-12-14 1973-07-27 Siemens Ag
FR2362945A1 (fr) * 1976-08-24 1978-03-24 Comp Generale Electricite Electrolyseur pour solutions basiques
DE2903407C2 (de) * 1979-01-30 1983-12-15 BOMIN Bochumer Mineralöl GmbH & Co, 4630 Bochum Verwendung einer aus Nickelpulver heißgepreßten oder gesinterten porösen Elektrode
US4289650A (en) * 1979-03-29 1981-09-15 Olin Corporation Cathode for chlor-alkali cells

Also Published As

Publication number Publication date
BR8201247A (pt) 1983-01-18
JPS57161078A (en) 1982-10-04
DD201701A5 (de) 1983-08-03
HU188056B (en) 1986-03-28
ES8303547A1 (es) 1983-02-01
AU547889B2 (en) 1985-11-07
AR228643A1 (es) 1983-03-30
DE3109183A1 (de) 1982-09-23
EP0059902A1 (de) 1982-09-15
CS159882A2 (en) 1985-08-15
US4447302A (en) 1984-05-08
ES510290A0 (es) 1983-02-01
DE3109183C2 (de) 1983-05-11
CS241504B2 (en) 1986-03-13
AU8079882A (en) 1982-09-16
CA1191815A (en) 1985-08-13
ATE14323T1 (de) 1985-08-15

Similar Documents

Publication Publication Date Title
DE2403573C2 (de) Verfahren zur Herstellung von Anoden
DE2636447C2 (de) Mangandioxidelektroden
DE10007448B4 (de) Aktivierte Kathode und Verfahren zu ihrer Herstellung
DE3122786A1 (de) "legierter edelmetallkatalysator fuer die katalytische redutkion von sauerstoff"
DE3507071C2 (de) Elektrode für die Elektrolyse und Verfahren zu ihrer Herstellung
DE2113676C2 (de) Elektrode für elektrochemische Prozesse
DE1928929A1 (de) Raney-Mischkatalysator
EP0059902B1 (de) Aus Nickelpulver heissgepresste hochporöse Elektrode für alkalische Wasserelektrolyseure
EP2379782B1 (de) Elektrochemisches verfahren zur reduktion molekularen sauerstoffs
DE69805579T2 (de) CO-tolerante Pt-Zn Legierung für Brennstoffzellen
DE2906821C2 (cs)
DE3780075T2 (de) Niedrigueberspannungs-elektroden fuer alkalische elektrolyte.
DE3110792C2 (de) Brennstoffzelle mit saurem Elektrolyten
LU88516A1 (de) Sauerstoff erzeugende Elektrode und Verfahren dieselbe herzustellen
DE3515742C2 (cs)
EP1316096A1 (de) Elektrode und kondensator mit der elektrode
DE4224290A1 (de) Verfahren zur Herstellung einer lithiumoxidhaltigen Nickeloxid-Kathode für eine Schmelzcarbonatbrennstoffzelle
DE19620504C2 (de) Elektrode für eine Schmelzkarbonatbrennstoffzelle und Verfahren zur Herstellung einer solchen sowie deren Verwendung
DE2903407C2 (de) Verwendung einer aus Nickelpulver heißgepreßten oder gesinterten porösen Elektrode
EP0148439A2 (de) Aktivierte Metallanoden sowie ein Verfahren zu deren Herstellung
EP0001778A2 (de) Elektroden für Elektrolysezwecke
DE10043865A1 (de) Verfahren zur Herstellung eines Katalysators
DE1952155A1 (de) Nickelanoden fuer Hochtemperaturbrennstoffzellen
DE2027482A1 (de) Verfahren zur Erhöhung der Aktivität von porösen Brennstoffzellenelektroden
DE2510078C3 (de) Gasdiffusionselektrode für elektrochemische Zellen

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): AT BE CH DE FR GB IT LI LU NL SE

17P Request for examination filed

Effective date: 19821027

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: SCHNAPKA, HERBERT, DR.

ITF It: translation for a ep patent filed
RBV Designated contracting states (corrected)

Designated state(s): AT BE CH FR GB IT LI LU NL SE

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): AT BE CH FR GB IT LI LU NL SE

REF Corresponds to:

Ref document number: 14323

Country of ref document: AT

Date of ref document: 19850815

Kind code of ref document: T

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19910214

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 19910221

Year of fee payment: 10

Ref country code: GB

Payment date: 19910221

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 19910225

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: LU

Payment date: 19910227

Year of fee payment: 10

ITTA It: last paid annual fee
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19910228

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19910305

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19910320

Year of fee payment: 10

EPTA Lu: last paid annual fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19920227

Ref country code: GB

Effective date: 19920227

Ref country code: AT

Effective date: 19920227

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19920228

Ref country code: BE

Effective date: 19920228

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Effective date: 19920229

Ref country code: CH

Effective date: 19920229

BERE Be: lapsed

Owner name: SCHNAPKA HERBERT

Effective date: 19920228

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19920901

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
GBPC Gb: european patent ceased through non-payment of renewal fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19921030

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

EUG Se: european patent has lapsed

Ref document number: 82101509.6

Effective date: 19920904