US20080011604A1 - Process and Device for Water Electrolysis Comprising a Special Oxide Electrode Material - Google Patents
Process and Device for Water Electrolysis Comprising a Special Oxide Electrode Material Download PDFInfo
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- US20080011604A1 US20080011604A1 US11/570,859 US57085905A US2008011604A1 US 20080011604 A1 US20080011604 A1 US 20080011604A1 US 57085905 A US57085905 A US 57085905A US 2008011604 A1 US2008011604 A1 US 2008011604A1
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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
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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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
- 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
- C25B11/077—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the compound being a non-noble metal oxide
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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
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
- H01M4/9025—Oxides specially used in fuel cell operating at high temperature, e.g. SOFC
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- 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
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Definitions
- the invention relates to a process for water electrolysis consisting in using an electrode comprising at least one special oxide material, particularly at high temperature.
- the invention also relates to a device for implementing such a water electrolysis process.
- the future use of hydrogen as an energy carrier requires the development of a process that provides large-scale production at low cost.
- the electrolysis of water enables hydrogen to be produced from water by using electrical energy to break down the water.
- the electrochemical reaction used is the reverse of the fuel cell principle.
- the water electrolysis process used industrially today is several decades old. It operates at a temperature of around 80 to 120° C. and the electrical efficiencies of said process are around 45 to 65%. This energy conversion efficiency is too low for this technique to be able to be used for the production of hydrogen as an energy carrier.
- the low operating temperature is partly responsible for the low energy conversion efficiency.
- a process operating at a high temperature i.e. generally at a temperature greater than or equal to 600° C.
- various techniques for producing hydrogen by high-temperature electrolysis of water described, for example, in the article “High-temperature steam electrolysis”, by E. Schouler, E. Fernandez and H. Bernard, RGE, March 1982) none have succeeded on an industrial scale, mainly due to the prohibitive cost, and also for the reasons explained below.
- the core of the electrochemical cell is composed of an anode or positive electrode, a cathode or negative electrode and a solid, ceramic-based electrolyte.
- the oxygen ions flow through the electrolyte from the cathode toward the anode.
- the solid electrolyte most commonly used is “yttria stabilized zirconia” or YSZ, also known as yttriated zirconia.
- the cathode which is the site of the reduction of water to produce hydrogen and O 2 ⁇ anions that will flow through the electrolyte, is most commonly a cermet (ceramic/metal composite) of the type where nickel is dispersed in the stabilized zirconia (YSZ), optionally doped with ruthenium Ru.
- the anode which releases the charges and which is the site of the oxidation of O 2 ⁇ ions to oxygen, is most commonly based on mixed-conducting oxides, such as SnO 2 -doped In 2 O 3 and lanthanum manganite LaMnO 3 doped with calcium or strontium.
- the process according to the invention is a water electrolysis process comprising the use of an electrode containing at least one oxide material of the following general formula: A 2 ⁇ x ⁇ y A′ x A′′ y M 1 ⁇ z M′ z O 4+ ⁇ , where: (1)
- A is a metal cation belonging to the group formed by lanthanides and/or alkali metals and/or alkaline-earth metals;
- A′ is at least one metal cation belonging to the group formed by lanthanides and/or alkali metals and/or alkaline-earth metals;
- A′′ is a cationic vacancy, that is to say a cation A and/or cation A′ vacancy;
- M is a metal belonging to the group formed by metals of transition elements
- M′ is at least one metal belonging to the group formed by metals of transition elements
- the previous formula therefore includes the case where x is equal to 0 or 2, that is to say the case where a single metal cation is present, and also, independently or not of the previous case, the case where z is equal to 0 or 1, that is to say the case where a single metal is present,
- A′ may represent several metal cations and M′ may also independently represent several metals; a person skilled in the art knows how to rewrite the formula (I) depending on the number of components.
- the previous formula therefore includes the case where ⁇ is equal to 0, that is to say the case where there is no oxygen superstoichiometry or substoichiometry.
- the previous formula therefore includes the case where y is equal to 0, that is to say the case where there is no cation vacancy.
- an oxygen superstoichiometry or substoichiometry coefficient ⁇ preferably an oxygen superstoichiometry coefficient ⁇ , with a value other than 0 may contribute advantageously to the ionic conductivity of the material.
- a value other than 0 may contribute advantageously to the ionic conductivity of the material.
- M and M′ are of mixed valency, that is to say that advantageously such metals contribute to the electronic conductivity of the material.
- such materials according to the invention have good thermal stability in terms of composition. This has been shown by TGA (thermogravimetric analysis) measurements in air, and confirmed by X-ray diffraction at temperature, on two materials which are Nd 1 95 NiO 4+ ⁇ and Nd 1 90 NiO 4+ ⁇ . Indeed, measurement of the oxygen superstoichiometry or substoichiometry coefficient ⁇ as a function of the temperature, over a range from room temperature, i.e. about 20° C., to 1000° C. does not show any changes and confirms that the loss of mass is directly and solely proportional to the variation of the oxygen content of the material.
- TGA thermogravimetric analysis
- the A′′ vacancies are randomly distributed.
- the electron diffraction pattern obtained by transmission electron microscopy of the material that is Nd 1 90 NiO 4+ ⁇ does not reveal any elongation or smearing of the main (001) spots, which reveals a perfect order along the c axis and the absence of intergrowths of the Ruddlesden-Popper type within the A 2 MO 4+ ⁇ stacks, thus confirming such a random distribution of the neodymium vacancies.
- lanthanide is understood according to the invention to mean lanthanum La or an element of the lanthanides group such as Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu and Y.
- alkali metal is understood according to the invention to mean an element other than hydrogen from group 1 (IUPAC version) of the Periodic Table of the Elements.
- alkaline-earth metal is understood according to the invention to mean an element from group 2 (IUPAC version) of the Periodic Table of the Elements.
- transition metal is understood according to the invention to mean an element from groups 3 to 12 (IUPAC version) of the Periodic Table of the Elements, including of course the elements from period 4 such as titanium Ti or gallium Ga, the elements from period 5 such as zirconium Zr or tin Sn and the elements from period 6 such as tantalum Ta or mercury Hg.
- the transition metal is an element from period 4.
- the material of the process according to the invention is advantageously characterized by very detailed measurements of (A and/or A′)/(M and/or M′) ratio(s) by Castaing microprobe (or EPMA, the acronym for, “Electron Probe Micxoanalysis”), which allows the exact composition of the material to be established and optionally the cation vacancy structure of said material to be evaluated.
- Castaing microprobe or EPMA, the acronym for, “Electron Probe Micxoanalysis”
- said process is such that:
- a and A′ are chosen independently from the group formed by lanthanum La, praseodymium Pr, strontium Sr, calcium Ca and neodymium Nd, preferably neodymium Nd, strontium Sr and calcium Ca, even more preferably neodymium Nd, and such that:
- M and M′ are chosen independently from the group formed by chromium Cr, manganese Mn, iron Fe, cobalt Co, nickel Ni and copper Cu, preferably nickel Ni and copper Cu, even more preferably nickel Ni.
- the number of type A cations is at least 2: A and A
- the number of type M cations is at least 2: M and M′.
- A is chosen from the group formed by lanthanum La, praseodymium Pr, and neodymium Nd, preferably neodymium Nd;
- A′ is chosen from the group formed by strontium Sr and calcium Ca, preferably calcium Ca;
- M is chosen from the group formed by chromium Cr, manganese Mn, iron Fe, cobalt Co, nickel Ni and copper Cu, preferably nickel Ni;
- M′ is chosen from the group formed by manganese Mn, iron Fe, copper Cu or cobalt Co, preferably copper Cu or manganese Mn.
- the material has a crystallographic structure of the K 2 NiF 4 type, as shown for example in “Inorganic Crystal Structures”, p. 30, by B. G. Hyde and S. Anderson, Wiley Interscience Publication (1988).
- the structure is thus formed of layers of oxygen-containing MO 6 octahedra shifted with respect to one another by 1 ⁇ 2 1 ⁇ 2 1 ⁇ 2, A atoms ensuring cohesion between the layers.
- additional oxygens O i may be inserted between these layers in the vacant interstitial sites.
- the material of the process according to the invention possesses an oxygen surface exchange coefficient k greater than 1 ⁇ 10 ⁇ 8 cm/s at 500° C. and greater than 2 ⁇ 10 ⁇ 6 cm/s at 900° C. for oxygen.
- the variation in said coefficient follows an Arrhenius law, which makes it easy to calculate this coefficient for another temperature in the temperature range of interest in the invention.
- the material of the process according to the invention possesses an electronic conductivity ⁇ e at least equal to 70 S/cm, preferably at least equal to 80 S/cm, even more preferably greater than 90 S/cm at 700° C.
- the material of the process according to the invention possesses an oxygen diffusion coefficient greater than 1 ⁇ 10 ⁇ 9 cm 2 /s at 500° C. and greater than 1 ⁇ 10 ⁇ 7 cm 2 /s at 900° C.
- the variation in said coefficient follows an Arrhenius law, which makes it easy to calculate this coefficient for another temperature in the temperature range of interest in the invention.
- the material of the process according to the invention possesses an oxygen surface exchange coefficient k greater than 1 ⁇ 10 ⁇ 8 cm/s at 500° C. and greater than 2 ⁇ 10 ⁇ 6 cm/s at 900° C. for oxygen, an electronic conductivity ⁇ e at least equal to 70 S/cm, preferably at least equal to 80 S/cm, even more preferably greater than 90 S/cm at 700° C. and an oxygen diffusion coefficient greater than 1 ⁇ 10 ⁇ 9 cm 2 /s at 500° C. and greater than 1 ⁇ 10 ⁇ 7 cm 2 /s at 900° C.
- said material is such that ⁇ is not equal to 0, preferably 0 ⁇ 0.25, even more preferably 0 ⁇ 0.10.
- the process according to the invention is implemented at a temperature greater than or equal to 600° C.
- the invention also relates to a device fox implementation of the process according to the invention.
- the invention thus relates to a water electrolyzer type device comprising at least one electrochemical cell comprising a solid electrolyte, a cathode and an anode, which comprises at least one oxide material of the following general formula: A 2 ⁇ x ⁇ y A′ x A′′ y M 1 ⁇ z M′ z O 4+ ⁇ , where: (1)
- A is a metal cation belonging to the group formed by lanthanides and/or alkali metals and/or alkaline-earth metals;
- A′ is at least one metal cation belonging to the group formed by lanthanides and/or alkali metals and/or alkaline-earth metals;
- A′′ is a cationic vacancy, that is to say a cation A and/or cation A′ vacancy;
- M is a metal belonging to the group formed by metals of transition elements
- M′ is at least one metal belonging to the group formed by metals of transition elements
- Said device also most often comprises at least one interconnector between two electrolysis cells Besides the anode, all the other parts of said device are generally components known to a person skilled in the art.
- the device according to the invention allows, with the use of the anode according to the invention having at the same time good electronic conductivity and good ionic conductivity when 6 is other than 0, and also good thermal stability and sufficient efficiency from an industrial point of view.
- the anode according to the invention preferably 0 ⁇ 0.25 more preferably 0 ⁇ 0.10.
- FIG. 1 is a graph showing, for the four materials used according to the invention, the oxygen diffusion coefficient D*(cm 2 /s) as a function of 1000/T (K ⁇ 1 ), where T is the temperature.
- FIG. 2 is a graph showing, for the four materials used according to the invention, the oxygen surface exchange coefficient k (cm/s) as a function of 1000/T (K ⁇ 1 ), where T is the temperature.
- FIG. 3 is a diagram of the principle for the electrolysis of water, as observed by the process and device according to the invention.
- FIGS. 1 and 2 are explained below in the examples.
- FIG. 3 is a diagram of the principle for the electrolysis of water, as observed by the process and device according to the invention.
- a device 1 can be seen therein, which is an electrochemical cell for the electrolysis of water, consisting of an anode 4 , a cathode 2 and an electrolyte 3 .
- An electrical connection is provided by a device 5 made up of a generator 6 and two electrical connecting wires 7 and 8 .
- Nd 1.95 NiO 4+ ⁇ and Nd 1.90 NiO 4+ ⁇ having y values equal to 0.05 and 0.10 respectively.
- These materials were synthesized indifferently by solid state reaction of Nd 2 O 3 and NiO oxides at 1100° C. or by soft chemistry or sol-gel methods, for example from the decomposition of neodymium and nickel nitrates in solution with final annealing at 11000 C.
- ⁇ e were measured at 700° C., equal to 100 S/cm and 80 S/cm respectively.
- Their oxygen surface exchange coefficients k were equal to 5.5 ⁇ 10 ⁇ 8 cm/s and 1.7 ⁇ 10 ⁇ 8 cm/s respectively at 500° C. and to 5.5 ⁇ 10 ⁇ 6 cm/s and 1.7 ⁇ 10 ⁇ 6 cm/s respectively at 900° C.
- Their oxygen diffusion coefficients were equal to 3.2 ⁇ 10 ⁇ 9 cm 2 /s and 5.2 ⁇ 10 ⁇ 9 cm 2 /s respectively at 500° C. and to 3.5 ⁇ 10 ⁇ 7 cm 2 /s and 2.5 ⁇ 10 ⁇ 7 cm 2 /s respectively at 900° C.
- Nd 2 NiO 4 was also used, having respectively x, y and z values equal to 0.
- This material was synthesized indifferently by solid state reaction of La 2 O 3 and NiO oxides at 1100° C. or by soft chemistry or sol-gel methods, for example from the decomposition of lanthanum and nickel nitrates in solution with final annealing at 1100° C.
- the electronic conductivity ⁇ e of said material at 700° C. was equal to 38 S/cm, and its oxygen surface exchange coefficient k was equal to 3 ⁇ 10 ⁇ 13 cm/s at 500° C. and 1.8 ⁇ 10 ⁇ 6 cm/s at 900° C., and its oxygen diffusion coefficient was 2.5 ⁇ 10 ⁇ 9 cm 2 /s and 2 ⁇ 10 ⁇ 7 cm 2 /s respectively at 500° C. and 900° C.
- La 2 NiO 4+ ⁇ was also used, having respectively x, y and z values equal to 0.
- This material was synthesized indifferently by solid state reaction of La 2 O 3 and NiO oxides at 1100° C. or by soft chemistry or sol-gel methods, for example from the decomposition of lanthanum and nickel nitrates in solution with final annealing at 1100° C.
- the electronic conductivity ⁇ e of said material at 700° C. was equal to 50 S/cm, and its oxygen surface exchange coefficient k was equal to 5 ⁇ 10 ⁇ 7 cm/s at 500° C.
- the electrochemical properties of these four materials were evaluated in a three-electrode assembly in a half-cell of electrode material/YSZ/electrode material type, where the counterelectrode and the working electrode are symmetrical, and are painted onto the electrolyte and annealed at 1100° C. for 2 hours.
- the platinum reference electrode was placed far from the other two electrodes.
- the behavior of this material was analyzed under conditions close to those of high temperature water electrolysis, that is to say under current and in a temperature range from 500 to 800° C.
- FIG. 1 is a graph showing, for the four materials used according to the invention, the oxygen diffusion coefficient D*(cm 2 /s) as a function of 1000/T (K ⁇ 1 ), where T is the temperature. Each curve is a straight line.
- the four materials according to the invention were Nd 2 NiO 4+ ⁇ , La 2 NiO 4+ ⁇ , Nd 1.95 NiO 4+ ⁇ and Nd 1.90 NiO 4+ ⁇ . It can be seen that in the temperature range of interest in the invention, the materials used according to the invention generally had, to within the measurement error, a high, and therefore beneficial, coefficient D*.
- FIG. 2 is a graph showing, for the four materials used according to the invention, the oxygen surface exchange coefficient k (cm/s) as a function of 1000/T (K ⁇ 1 ), where T is the temperature. Each curve is a straight line.
- the four materials according to the invention were Nd 2 NiO 4+ ⁇ , La 2 NiO 4+ ⁇ , Nd 1.95 NiO 4+ ⁇ and Nd 1.90 NiO 4+ ⁇ . It can be seen that in the temperature range of interest in the invention, the materials used according to the invention generally had a high, and therefore beneficial, coefficient k.
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Abstract
Description
- The invention relates to a process for water electrolysis consisting in using an electrode comprising at least one special oxide material, particularly at high temperature. The invention also relates to a device for implementing such a water electrolysis process.
- The future use of hydrogen as an energy carrier requires the development of a process that provides large-scale production at low cost. The electrolysis of water enables hydrogen to be produced from water by using electrical energy to break down the water. The electrochemical reaction used is the reverse of the fuel cell principle. The water electrolysis process used industrially today is several decades old. It operates at a temperature of around 80 to 120° C. and the electrical efficiencies of said process are around 45 to 65%. This energy conversion efficiency is too low for this technique to be able to be used for the production of hydrogen as an energy carrier.
- The low operating temperature is partly responsible for the low energy conversion efficiency. A process operating at a high temperature (i.e. generally at a temperature greater than or equal to 600° C.) has a better electrical efficiency since the reactions at the electrodes are facilitated and because thermal energy may also be used in the electrochemical conversion process. Among the various techniques for producing hydrogen by high-temperature electrolysis of water (described, for example, in the article “High-temperature steam electrolysis”, by E. Schouler, E. Fernandez and H. Bernard, RGE, March 1982) none have succeeded on an industrial scale, mainly due to the prohibitive cost, and also for the reasons explained below.
- The core of the electrochemical cell is composed of an anode or positive electrode, a cathode or negative electrode and a solid, ceramic-based electrolyte. The oxygen ions flow through the electrolyte from the cathode toward the anode. The solid electrolyte most commonly used is “yttria stabilized zirconia” or YSZ, also known as yttriated zirconia. The cathode, which is the site of the reduction of water to produce hydrogen and O2− anions that will flow through the electrolyte, is most commonly a cermet (ceramic/metal composite) of the type where nickel is dispersed in the stabilized zirconia (YSZ), optionally doped with ruthenium Ru. The anode, which releases the charges and which is the site of the oxidation of O2− ions to oxygen, is most commonly based on mixed-conducting oxides, such as SnO2-doped In2O3 and lanthanum manganite LaMnO3 doped with calcium or strontium.
- The production of hydrogen requires the coupling, as a battery, of many elementary cells, the creation of interconnections that allow two contiguous cells to be connected electrically while ensuring a seal between two anode and cathode compartments, is generally achieved with a specific material generally known to a person skilled in the art, for example with a Cr—MgO—Al2O3 cermet-type material covered in platinum on the oxygen (anode) side and with nickel on the hydrogen (cathode) side. Lastly the geometry of such batteries is generally of tubular or planar type, preferably tubular.
- The only high-temperature process experimented with today (the process known as “Hot Elly”, called the Dornier System process in the aforementioned article) relates to an electrolyzer that operates at 1000° C. Such an electrolyzer is of tubular geometry and uses small concentric cylindrical tubes, predominantly made of zirconia. The electrodes (nickel-yttriated zirconia cermet for the cathode and lanthanum manganite for the anode) are deposited by spraying. But the materials and the manufacturing process used are too costly for a commercial application to be reasonably envisaged.
- It is in order to solve these problems of the prior art that another type of oxide material must be used as the electrode of at least one electrochemical cell for the electrolysis of water. It is this that the process according to the invention achieves.
- The process according to the invention is a water electrolysis process comprising the use of an electrode containing at least one oxide material of the following general formula:
A2−x−yA′xA″yM1−zM′zO4+δ, where: (1) - A is a metal cation belonging to the group formed by lanthanides and/or alkali metals and/or alkaline-earth metals;
- A′ is at least one metal cation belonging to the group formed by lanthanides and/or alkali metals and/or alkaline-earth metals;
- A″ is a cationic vacancy, that is to say a cation A and/or cation A′ vacancy;
- M is a metal belonging to the group formed by metals of transition elements;
- M′ is at least one metal belonging to the group formed by metals of transition elements;
- said material being such that
- 0≦y<0.30, preferably 0≦y≦0.20;
- −0.1≦δ<0.25, preferably 0≦δ<0.25, more preferably 0≦δ<0.10;
- 0≦x≦1; and
- 0≦z≦1.
- The previous formula therefore includes the case where x is equal to 0 or 2, that is to say the case where a single metal cation is present, and also, independently or not of the previous case, the case where z is equal to 0 or 1, that is to say the case where a single metal is present,
- A′ may represent several metal cations and M′ may also independently represent several metals; a person skilled in the art knows how to rewrite the formula (I) depending on the number of components.
- The previous formula therefore includes the case where δ is equal to 0, that is to say the case where there is no oxygen superstoichiometry or substoichiometry.
- The previous formula therefore includes the case where y is equal to 0, that is to say the case where there is no cation vacancy.
- In addition, the presence of an oxygen superstoichiometry or substoichiometry coefficient δ, preferably an oxygen superstoichiometry coefficient δ, with a value other than 0 may contribute advantageously to the ionic conductivity of the material. In such a case, preferably 0<δ<0.25, more preferably 0<δ<0.10.
- According to a particularly preferred embodiment of the invention, M and M′ are of mixed valency, that is to say that advantageously such metals contribute to the electronic conductivity of the material.
- Advantageously, such materials according to the invention have good thermal stability in terms of composition. This has been shown by TGA (thermogravimetric analysis) measurements in air, and confirmed by X-ray diffraction at temperature, on two materials which are Nd1 95NiO4+δ and Nd1 90NiO4+δ. Indeed, measurement of the oxygen superstoichiometry or substoichiometry coefficient δ as a function of the temperature, over a range from room temperature, i.e. about 20° C., to 1000° C. does not show any changes and confirms that the loss of mass is directly and solely proportional to the variation of the oxygen content of the material.
- Advantageously, when according to an embodiment of the invention y is other than 0, the A″ vacancies are randomly distributed. Indeed, the electron diffraction pattern obtained by transmission electron microscopy of the material that is Nd1 90NiO4+δ does not reveal any elongation or smearing of the main (001) spots, which reveals a perfect order along the c axis and the absence of intergrowths of the Ruddlesden-Popper type within the A2MO4+δ stacks, thus confirming such a random distribution of the neodymium vacancies.
- The term “lanthanide” is understood according to the invention to mean lanthanum La or an element of the lanthanides group such as Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu and Y. The term “alkali metal” is understood according to the invention to mean an element other than hydrogen from group 1 (IUPAC version) of the Periodic Table of the Elements. The term “alkaline-earth metal” is understood according to the invention to mean an element from group 2 (IUPAC version) of the Periodic Table of the Elements. The term “transition metal” is understood according to the invention to mean an element from
groups 3 to 12 (IUPAC version) of the Periodic Table of the Elements, including of course the elements fromperiod 4 such as titanium Ti or gallium Ga, the elements fromperiod 5 such as zirconium Zr or tin Sn and the elements fromperiod 6 such as tantalum Ta or mercury Hg. Preferably, according to the invention, the transition metal is an element fromperiod 4. - When y is other than 0, the material of the process according to the invention is advantageously characterized by very detailed measurements of (A and/or A′)/(M and/or M′) ratio(s) by Castaing microprobe (or EPMA, the acronym for, “Electron Probe Micxoanalysis”), which allows the exact composition of the material to be established and optionally the cation vacancy structure of said material to be evaluated.
- In a preferred embodiment of the invention, said process is such that:
- A and A′ are chosen independently from the group formed by lanthanum La, praseodymium Pr, strontium Sr, calcium Ca and neodymium Nd, preferably neodymium Nd, strontium Sr and calcium Ca, even more preferably neodymium Nd, and such that:
- M and M′ are chosen independently from the group formed by chromium Cr, manganese Mn, iron Fe, cobalt Co, nickel Ni and copper Cu, preferably nickel Ni and copper Cu, even more preferably nickel Ni.
- In the particular cases according to the invention where x is not equal to 0 or 2, and z is not equal to 0 or 1, the number of type A cations is at least 2: A and A, and the number of type M cations is at least 2: M and M′.
- In such a case, and in a more general way, preferably:
- A is chosen from the group formed by lanthanum La, praseodymium Pr, and neodymium Nd, preferably neodymium Nd;
- A′ is chosen from the group formed by strontium Sr and calcium Ca, preferably calcium Ca;
- M is chosen from the group formed by chromium Cr, manganese Mn, iron Fe, cobalt Co, nickel Ni and copper Cu, preferably nickel Ni; and
- M′ is chosen from the group formed by manganese Mn, iron Fe, copper Cu or cobalt Co, preferably copper Cu or manganese Mn.
- In a particularly preferred embodiment according to the invention, the material has a crystallographic structure of the K2NiF4 type, as shown for example in “Inorganic Crystal Structures”, p. 30, by B. G. Hyde and S. Anderson, Wiley Interscience Publication (1988). The structure is thus formed of layers of oxygen-containing MO6 octahedra shifted with respect to one another by ½ ½ ½, A atoms ensuring cohesion between the layers. When additional oxygens Oi are present, they may be inserted between these layers in the vacant interstitial sites.
- In a preferred embodiment, the material of the process according to the invention possesses an oxygen surface exchange coefficient k greater than 1×10−8 cm/s at 500° C. and greater than 2×10−6 cm/s at 900° C. for oxygen. The variation in said coefficient follows an Arrhenius law, which makes it easy to calculate this coefficient for another temperature in the temperature range of interest in the invention.
- In a preferred embodiment, independently or not of the previous embodiment, the material of the process according to the invention possesses an electronic conductivity σe at least equal to 70 S/cm, preferably at least equal to 80 S/cm, even more preferably greater than 90 S/cm at 700° C.
- In a preferred embodiment, independently or not of the previous embodiment, the material of the process according to the invention possesses an oxygen diffusion coefficient greater than 1×10−9 cm2/s at 500° C. and greater than 1×10−7 cm2/s at 900° C. The variation in said coefficient follows an Arrhenius law, which makes it easy to calculate this coefficient for another temperature in the temperature range of interest in the invention.
- In a preferred embodiment, the material of the process according to the invention possesses an oxygen surface exchange coefficient k greater than 1×10−8 cm/s at 500° C. and greater than 2×10−6 cm/s at 900° C. for oxygen, an electronic conductivity σe at least equal to 70 S/cm, preferably at least equal to 80 S/cm, even more preferably greater than 90 S/cm at 700° C. and an oxygen diffusion coefficient greater than 1×10−9 cm2/s at 500° C. and greater than 1×10−7 cm2/s at 900° C.
- In an embodiment of the process according to the invention, said material is such that δ is not equal to 0, preferably 0<δ<0.25, even more preferably 0<δ<0.10.
- Preferably, the process according to the invention is implemented at a temperature greater than or equal to 600° C.
- The invention also relates to a device fox implementation of the process according to the invention.
- The invention thus relates to a water electrolyzer type device comprising at least one electrochemical cell comprising a solid electrolyte, a cathode and an anode, which comprises at least one oxide material of the following general formula:
A2−x−yA′xA″yM1−zM′zO4+δ, where: (1) - A is a metal cation belonging to the group formed by lanthanides and/or alkali metals and/or alkaline-earth metals;
- A′ is at least one metal cation belonging to the group formed by lanthanides and/or alkali metals and/or alkaline-earth metals;
- A″ is a cationic vacancy, that is to say a cation A and/or cation A′ vacancy;
- M is a metal belonging to the group formed by metals of transition elements;
- M′ is at least one metal belonging to the group formed by metals of transition elements;
- said material being such that
- 0≦y<0.30, preferably 0≦y≦0.20;
- −0.1≦δ<0.25, preferably 0≦δ<0.25, more preferably 0≦δ<0.10;
- 0≦x≦1; and
- 0≦z≦1.
- Said device also most often comprises at least one interconnector between two electrolysis cells Besides the anode, all the other parts of said device are generally components known to a person skilled in the art.
- Advantageously, the device according to the invention allows, with the use of the anode according to the invention having at the same time good electronic conductivity and good ionic conductivity when 6 is other than 0, and also good thermal stability and sufficient efficiency from an industrial point of view. In such a case, preferably 0<δ<0.25 more preferably 0<δ<0.10.
- The invention will be better understood and other features and advantages will appear on reading the description that follows, given without limitation, with reference to FIGS. 1 to 3.
-
FIG. 1 is a graph showing, for the four materials used according to the invention, the oxygen diffusion coefficient D*(cm2/s) as a function of 1000/T (K−1), where T is the temperature. -
FIG. 2 is a graph showing, for the four materials used according to the invention, the oxygen surface exchange coefficient k (cm/s) as a function of 1000/T (K−1), where T is the temperature. -
FIG. 3 is a diagram of the principle for the electrolysis of water, as observed by the process and device according to the invention. -
FIGS. 1 and 2 are explained below in the examples, -
FIG. 3 is a diagram of the principle for the electrolysis of water, as observed by the process and device according to the invention. Adevice 1 can be seen therein, which is an electrochemical cell for the electrolysis of water, consisting of ananode 4, acathode 2 and anelectrolyte 3. An electrical connection is provided by adevice 5 made up of agenerator 6 and two electrical connectingwires - The examples that follow illustrate the invention without in any way limiting the scope thereof.
- Two materials were synthesized: Nd1.95NiO4+δ, and Nd1.90NiO4+δ having y values equal to 0.05 and 0.10 respectively. These materials were synthesized indifferently by solid state reaction of Nd2O3 and NiO oxides at 1100° C. or by soft chemistry or sol-gel methods, for example from the decomposition of neodymium and nickel nitrates in solution with final annealing at 11000C. Their oxygen superstoichiometry values were equal to δ=0.15 and δ=0.06 respectively, determined by chemical analysis of Ni3+ (iodometry)
- Their electronic conductivities σe were measured at 700° C., equal to 100 S/cm and 80 S/cm respectively. Their oxygen surface exchange coefficients k were equal to 5.5×10−8 cm/s and 1.7×10−8 cm/s respectively at 500° C. and to 5.5×10−6 cm/s and 1.7×10−6 cm/s respectively at 900° C. Their oxygen diffusion coefficients were equal to 3.2×10−9 cm2/s and 5.2×10−9 cm2/s respectively at 500° C. and to 3.5×10−7 cm2/s and 2.5×10−7 cm2/s respectively at 900° C. The percentages of Ni3+ cations at 700° C., determined by TGA (thermogravimetric analysis) in air, were equal to 35% and 28% respectively. The variation in the oxygen stoichiometry within this temperature range, in which the operating temperature of the electrolyzer lies, was small and had no influence over the thermal expansion coefficient, which remained constant and equal to 12.7×10−6 K−1.
- A material Nd2NiO4 was also used, having respectively x, y and z values equal to 0. This material was synthesized indifferently by solid state reaction of La2O3 and NiO oxides at 1100° C. or by soft chemistry or sol-gel methods, for example from the decomposition of lanthanum and nickel nitrates in solution with final annealing at 1100° C. The oxygen superstoichiometry value was equal to δ=0.22, determined by chemical analysis of Ni3+ (iodometry). The electronic conductivity σe of said material at 700° C. was equal to 38 S/cm, and its oxygen surface exchange coefficient k was equal to 3×10−13 cm/s at 500° C. and 1.8×10−6 cm/s at 900° C., and its oxygen diffusion coefficient was 2.5×10−9 cm2/s and 2×10−7 cm2/s respectively at 500° C. and 900° C.
- A material La2NiO4+δ was also used, having respectively x, y and z values equal to 0. This material was synthesized indifferently by solid state reaction of La2O3 and NiO oxides at 1100° C. or by soft chemistry or sol-gel methods, for example from the decomposition of lanthanum and nickel nitrates in solution with final annealing at 1100° C. The oxygen superstoichiometry value was equal to δ=0.16, determined by chemical analysis of Ni3+ (iodometry). The electronic conductivity σe of said material at 700° C. was equal to 50 S/cm, and its oxygen surface exchange coefficient k was equal to 5×10−7 cm/s at 500° C. and 5×10−6 cm/s at 900° C., and its oxygen diffusion coefficient was 4.5×10−9 cm2/s and 2.2×10−1 cm2/s respectively at 500° C. and 900° C. The percentage of Ni3+ cations at 700° C., determined by TGA (thermogravimetric analysis) in air, was equal to 26%. Its thermal expansion coefficient remained constant with the temperature and was equal to 13.0×10−6 K−1.
- The electrochemical properties of these four materials were evaluated in a three-electrode assembly in a half-cell of electrode material/YSZ/electrode material type, where the counterelectrode and the working electrode are symmetrical, and are painted onto the electrolyte and annealed at 1100° C. for 2 hours. The platinum reference electrode was placed far from the other two electrodes. The behavior of this material was analyzed under conditions close to those of high temperature water electrolysis, that is to say under current and in a temperature range from 500 to 800° C.
-
FIG. 1 is a graph showing, for the four materials used according to the invention, the oxygen diffusion coefficient D*(cm2/s) as a function of 1000/T (K−1), where T is the temperature. Each curve is a straight line. The four materials according to the invention were Nd2NiO4+δ, La2NiO4+δ, Nd1.95NiO4+δ and Nd1.90NiO4+δ. It can be seen that in the temperature range of interest in the invention, the materials used according to the invention generally had, to within the measurement error, a high, and therefore beneficial, coefficient D*. -
FIG. 2 is a graph showing, for the four materials used according to the invention, the oxygen surface exchange coefficient k (cm/s) as a function of 1000/T (K−1), where T is the temperature. Each curve is a straight line. The four materials according to the invention were Nd2NiO4+δ, La2NiO4+δ, Nd1.95NiO4+δ and Nd1.90NiO4+δ. It can be seen that in the temperature range of interest in the invention, the materials used according to the invention generally had a high, and therefore beneficial, coefficient k.
Claims (11)
A2−x−yA′xA″yM1−zM′zO4+δ, where:
A2−x−yA′xA″yM1−zM′zO4+δ, where:
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FR0406839 | 2004-06-23 | ||
FR0406839A FR2872174B1 (en) | 2004-06-23 | 2004-06-23 | METHOD AND DEVICE FOR ELECTROLYSIS OF WATER COMPRISING A PARTICULAR ELECTRODE OXIDE MATERIAL |
PCT/FR2005/001556 WO2006008390A2 (en) | 2004-06-23 | 2005-06-21 | Method and device for water electrolysis comprising a special oxide electrode material |
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US (1) | US20080011604A1 (en) |
EP (1) | EP1774061B1 (en) |
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US20110226632A1 (en) * | 2010-03-19 | 2011-09-22 | Emily Barton Cole | Heterocycle catalyzed electrochemical process |
US8313634B2 (en) | 2009-01-29 | 2012-11-20 | Princeton University | Conversion of carbon dioxide to organic products |
US8500987B2 (en) | 2010-03-19 | 2013-08-06 | Liquid Light, Inc. | Purification of carbon dioxide from a mixture of gases |
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- 2005-06-21 WO PCT/FR2005/001556 patent/WO2006008390A2/en not_active Application Discontinuation
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FR2872174A1 (en) | 2005-12-30 |
FR2872174B1 (en) | 2007-06-15 |
WO2006008390A2 (en) | 2006-01-26 |
EP1774061A2 (en) | 2007-04-18 |
EP1774061B1 (en) | 2017-05-03 |
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