• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
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    • 专利摘要:

    公开号:AT510156A4
    申请号:T0165510
    申请日:2010-10-04
    公开日:2012-02-15
    发明作者:
    申请人:Brunauer Georg；
    IPC主号:
    专利说明:

    - 1 • fl ······ 4
    The invention relates to a photoelectrochemical cell for solar-powered decomposition of a starting material, in particular water or carbon dioxide, in a product gas bound therein, in particular hydrogen or carbon monoxide, with a feed line for the starting material and a derivative for the recovered product gas, with a exposed during operation of solar radiation first electrode of a photoelectrically active material and a second electrode, wherein the electrodes are connected in a closed circuit via an electron conductor for transporting excited by the solar radiation in the first electrode and an ion conductor for the transport of ions resulting from the decomposition of the starting material ,
    The invention further relates to a process for the solar-powered decomposition of a starting material, in particular water or carbon dioxide, into a product gas bound therein, in particular hydrogen or carbon monoxide, wherein charge carriers in the form of electron-hole pairs are excited in a photoelectrically active first electrode by means of solar radiation. wherein the excited electrons are conducted to a second electrode and one of the electrodes is supplied with the starting material which is decomposed by the excited charge carriers, producing ions which are transported in a closed circuit to the respective other electrode, wherein the product gas recovered is derived ,
    Solar energy represents one of the most important renewable primary energy sources, which exceeds the world energy demand many times over. The efficient use of solar energy, however, is difficult because the energy density of solar radiation is low compared to fossil fuels. Another problem is the changing availability of solar energy. Thus, a major challenge is to convert solar energy as efficiently as possible into a storable and transportable secondary energy source. Great efforts have already been made to convert solar energy into chemically bound energy. Hydrogen has become increasingly important as a secondary energy source in the recent past. In view of the serious effects of - 2 * · »· · · · t ··· ·» ···················································
    Greenhouse gases are also being sought for solutions to convert carbon dioxide into carbon monoxide efficiently.
    For the decomposition of water into molecular hydrogen (and the by-produced oxygen), photoelectrochemical cells (PEC - "Photoelectrochemical Cell") have been developed in the art. Such a cell is described for example in US 2008/0131762 Al.
    The photoelectrochemical cells usually consist of a photo-anode, of a semiconductive material which is exposed to the generation of electron-hole pairs solar radiation, and at least one cathode forming a counter electrode. The electrodes are immersed in an electrolytic solution. For closing the circuit also an electrically conductive connection between the electrodes is provided. The solar generated at the photo-anode current flows to the opposite cathode to react with H + ions to molecular hydrogen. This technique is based on the internal photoelectric effect, whereby the short-wave radiation components, which can excite electron-hole pairs in the semiconductor, are converted into molecular hydrogen - and thus into chemical energy.
    The conversion of solar energy into chemical energy is not very efficient in the known photoelectrochemical cells, since only the short-wave radiation components whose energy is sufficient to excite the electron-hole pairs, can be used, the long-wave radiation components whose photon energy is less than the band gap of the semiconducting Photoelectrode is, represent a not useful for the conversion of the starting material thermal energy. In the known PECs, the heat input by the solar radiation is even undesirable because the liquid electrolytes used can be chemically unstable at higher temperatures. A significant disadvantage of the known photoelectrochemical cells (PEC) is that photocorrosion can occur at the photoelectrode, which is understood to mean the decomposition of the photoelectrode accommodated in the aqueous electrolyte under the influence of solar radiation. When photocorrosion occurs, the photoelectrically active electrode is oxidized, whereby electrode material * * * * «· ···· · * · Φ» ···· * · · t φ t ····· · · · · · · · ·· · + ·· ♦ · # · # 9 · »- 3 - goes into solution. Despite intensive research, it has not been satisfactorily achieved to ensure the stability of the photoactive electrode material in the liquid electrolyte under irradiation.
    In addition, in the state of the art, high-temperature electrolysis was developed to recover hydrogen, in which steam is converted into hydrogen and oxygen at temperatures of about 800 ° to 1000 ° C. In this case, an electrical voltage is applied to electrically conductive electrodes, between which an ion-conducting solid electrolyte (for example, calcium-yttrium-zirconium oxide or a perovskite) is arranged. The implementation of the water vapor at elevated temperature has a comparatively high efficiency. However, the electrolysis of water basically has the disadvantage that power must be supplied from an external power source. Although this current can be generated with a photovoltaic system, which uses analogous to the photoelectrochemical cells only the short-wave radiation components for power generation; However, the thermal energy of the long-wave radiation components is lost or is not available for electrolysis. In addition, transmission losses are unavoidable when the photovoltaic power is passed to the high-temperature electrolysis apparatus.
    Accordingly, the object of the present invention is to provide a device or a method of the type mentioned, which or which allows efficient use of solar energy for the production of product gases. In addition, the disadvantages occurring in known photoelectrochemical cells or the associated methods should be avoided or reduced.
    This object is achieved by a photoelectrochemical cell having the features of the characterizing part of claim 1 and a method having the features of the characterizing part of claim 12. Preferred embodiments of the invention are indicated in the dependent claims.
    Accordingly, between the electrodes a heat-resistant solid ······································································································. A material which forms an ion-conducting connection between the electrodes is arranged. The use of the heat-resistant solid electrolyte allows the processes taking place in the photo-electrochemical cell, i. at least the excitation of the photo-electrode, the decomposition of the starting material and the ion transport through the electrolyte, at a room temperature substantially increased operating temperature, suitably more than 300 ° Celsius to perform. As a result, a considerable increase in efficiency in the recovery of the product gas can be achieved, as will be explained below. The solar radiation has short-wave radiation components whose photon energy is greater than the band gap between the valence band and the conduction band of the semiconducting material of the first electrode. The short-wave radiation excites in the photoactive first electrode by means of the internal photoelectron electron-hole pairs; the electrons excited in the first electrode are conducted via the current conductor to the opposite second electrode in order to decompose the starting material into the product gas. The solar radiation also has long-wave radiation components which do not overcome the band gap in the photoactive first electrode and thus can not excite electrons. These proportions therefore act - as does the energy of the short-wave components beyond the band gap - as thermal energy, which remained unused in known photoelectrochemical cells or was avoided as much as possible as an undesirable side effect. In contrast, the thermal energy is converted in the inventive technique into internal energy of the photo-electrochemical cell to increase the operating temperature. The heat-resistant solid electrolyte withstands the increased operating temperatures due to the heat input through the long-wave radiation components. In addition, this avoids the often occurring in aqueous electrolyte photocorrosion. The increased operating temperature has, on the one hand, the advantage that the band gap of the semiconducting material of the pho-active first electrode is reduced. This relationship between temperature and bandgap is known in the art as a model equation by Varshni. As the operating temperature increases, the spectrum of solar radiation usable for exciting electrons in the photoelectrically active first electrode is widened to the long-wave range, so that
    the charge carrier density generated in the photoactive first electrode is substantially increased. Thus, the current conducted to the opposite second electrode can be increased to improve the conversion of the starting material. An increased operating temperature, which is only made possible by the use of heat-resistant solid materials for the electrolyte, has the further advantage that the thermodynamic decomposition voltage (also chemical potential or Gibbs energy) of the starting material is reduced, including the minimum required difference between the Electrode potentials is understood. For water separation, the standard voltage potential at room temperature (298.15 Kelvin) and an ambient pressure of 1 bar is approx. 1.23 V, which in this case corresponds to a chemical potential or Gibbs energy of 1.23 eV. With an increase in the operating temperature to preferably 500 ° to 900 ° Celsius (773 - 1,175 Kelvin), the voltage potential of water drops to 0.9-1 V. The photoelectrochemical cell is configured to conserve the operating temperature to a high level by the thermal energy of the solar radiation to take advantage of a lower decomposition voltage for the precursor and the increased electron density in the photoactive first electrode. Thus, a particularly efficient implementation of solar energy can be achieved by the radiation components not involved in the excitation of electron-hole pairs are used to heat the photoelectrochemical cell. On the other hand, by the use of the solid electrolyte, photocorrosion of the photoelectrically active first electrode due to solar radiation is reliably prevented even at an elevated operating temperature. Thus, an electrolysis technique is provided which relates the required for the decomposition of the starting material current from the solar excitation of the photoactive first electrode, wherein with regard to increased operating temperatures as a ion conductor, a solid electrolyte is provided. As a result, the efficiency compared to known photoelectrochemical cells, which can only use a narrow bandwidth of the radiation spectrum, be significantly increased. On the other hand, an increase in efficiency compared to electrolysis apparatuses with external power supply to maintain the potential difference between the electrodes is achieved. Thus, a photoelek- * * ♦ ♦ ··· ¥ Ψ ♦ · · · · · · + + + + + + + + + The thermoelectric cell or an associated photoelectric-thermochemical process is provided which comprises the photoelectric charge carrier generation known from conventional photoelectrochemical cells with a thermally assisted chemical decomposition of the starting material of the heat-resistant solid electrolyte is made possible - combined.
    In order to ensure the thermal stability of the photoelectrochemical cell in a wide temperature range, in particular for operating temperatures of more than 300 ° Celsius, it is favorable if the electrolyte of a solid oxide material, in particular zirconium dioxide (ZrO 2) or a lanthanum mixed oxide, preferably Lanthanum zirconate (LaZr03) or lanthanum nate (La-Ce03). These materials make it possible to operate the photoelectrochemical cell at operating temperatures of at least more than 300 ° C to utilize a significant reduction in chemical potential in decomposition of the precursor and increased electron yield in the photoactive material of the first electrode. The solid oxide material used for the ionic conductor depends on the type of ions transported; ZrO 2 is expediently provided as solid electrolyte for the transport of O 2 'ions, which allows operation of the photoelectrochemical cell at operating temperatures of preferably 700-1000 ° Celsius. For a transport of H + ions, an electrolyte of a lanthanum mixed oxide, in particular lanthanum zirconate or lanthanum carbonate, is preferably provided, which allows the use of the cell in a preferred temperature range of 300-700 ° Celsius. When the photoelectrochemical cell is used to reduce carbon dioxide, only 02'-ion conduction is possible, which is made possible with the corresponding solid oxide material; Depending on the version, water separation may involve the transport of H + ions or O 2 - ions, for which either an H + ion or an O 2 -ion conductive solid oxide material is provided.
    To improve the ion-conducting properties of the solid oxide material, it is advantageous if the solid oxide material is doped with a rare earth metal, in particular with yttrium. - 7 · «· * ····
    In order to obtain a thermally stable photoelectrode with high electron yield under sunlight, it is advantageous if the first electrode is made as an anode from a transition metal oxide (MeOx), preferably Fe 2 O 3, CoO, Cu 2 O, NiO, SnO 2, TiO 2, WO 3 or ZnO.
    For the efficient decomposition of the starting material, it is advantageous if the second electrode is made as a cathode of a catalytically active material, in particular RuO 2, LaSrMnO 3, Pt, a metal-ceramic mixture, preferably Ni-YSZ, or Ni.
    Conventional electrolysis equipment necessarily requires an external power supply to generate a potential difference between the electrodes. In contrast, the charge carriers in the device according to the invention are excited by irradiation of the photoactive first electrode. However, in order to reduce the electron-hole recombination in the first electrode, it may be desirable for the electron conductor to have a voltage or current source to assist in the transport of the electrons excited by the solar radiation.
    Upon excitation of the photoactive first electrode, electron-hole pairs are generated. The charge carriers can recombine with the ions produced in the reaction of the starting material to form a by-product. Appropriately, it is therefore provided that one of the electrodes is connected to a discharge for a gaseous by-product, in particular oxygen, resulting from the decomposition of the starting material.
    To improve the ion transport, it is advantageous if a catalyst layer, in particular of Pt, RuO 2, Ni, Ni-YSZ, or LaSrMnO 3, is arranged between one of the electrodes and the electrolyte. YSZ stands here as an abbreviation for "Yttria-stabilized zirconia", which is understood to mean a zirconium-oxide-based ceramic material. The material for the catalyst layer will vary depending on the nature of the ions being transported, i. in particular 02 'or H + ions, chosen such that the desired catalytic effect is achieved. - 8 - ·· * · * ft • * Μ * 1 ft • ft ft ft ••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••
    * # # # MM
    In order to increase the electron yield during the excitation of the photoactive first electrode, it is favorable if the first electrode is assigned a device for focusing the incident solar radiation, which is adapted to reduce the intensity of a radiation focused on the first electrode by at least the times, preferably by at least 50 times, to increase the incident solar radiation. The concentrated solar radiation makes it possible to increase the heat input into the photo-electrochemical cell in order to keep the operating temperature at a substantially higher than room temperature level, in particular more than 300 ° Celsius. Thus, the thermal energy of solar radiation - which has been neglected in conventional cells of this type - be specifically exploited. The device for concentrating the incident solar radiation is in particular designed to automatically maintain the increased operating temperature of the photoelectrochemical cell. In addition, the charge density in the photoactive material of the first electrode can be considerably increased by the focused solar radiation. Preferably, a surface-focusing device for bundling the solar radiation is provided, which includes, for example, solar tower power plants, which have a heliostat and a receiver. Alternatively, a line-focusing device can be arranged, expediently a parabolic trough collector system or a Fresnel collector system.
    In a preferred embodiment of the invention it is provided that the electrodes and the electrolyte are accommodated to obtain a panel in a flat housing, which has a light-transmitting entrance window covering the first electrode, in particular a glass pane. The photoelectrically active first electrode is preferably designed as a large-area plate, which can be oriented in the direction of the incident solar radiation. The panel is - similar to a photovoltaic system - a mechanically stable, compact arrangement that can be easily and quickly assembled. In an alternative preferred embodiment of the invention it is provided that at least the solar radiation facing photoactive first electrode is curved. Preferably, the photoelectrical * * t ·· * · ** «·» · · · · · »♦ ♦» · * M M M M M M M M M M M | M i * * - 9 - mixed cell in a substantially cylindrical shape, wherein the entrance window, the first electrode, the electrolyte and the second electrode are formed by corresponding hollow cylindrical layers.
    In order to maintain an elevated operating temperature, it is favorable if the housing is encased by an insulating body which has a recess corresponding to the entrance window. Thus, the thermal energy of solar radiation in the cell can be converted into internal energy with high efficiency to increase the operating temperature of the cell.
    With the method according to the invention, the same advantages as with the device according to the invention are achieved, so that in order to avoid repetition, reference may be made to the above statements.
    The excitation of the first electrode, the ion transport between the electrodes and the decomposition of the starting material is preferably carried out at an operating temperature of more than 300 ° Celsius, preferably more than 500 ° Celsius. These operating temperatures make it possible, on the one hand, to considerably lower the bandgap of the semiconducting material of the photoactive first electrode, so that the radiation components of the solar radiation usable for excitation of electron-hole pairs are widened in the direction of long-wave radiation. In addition, the chemical potential for the decomposition of the starting material is lowered, so that a more efficient conversion of the starting material is made possible in the product gas.
    When the first electrode is irradiated with concentrated solar radiation whose intensity is increased by at least 30 times, preferably by at least 50 times, with respect to the intensity of the incident solar radiation, in the first electrode more electrons are lifted into the conduction band the electron conductor to the second electrode are passed to decompose the starting material into the product gas and the corresponding ions. The focusing of the solar radiation also has the advantage that the operating temperature can be kept in the desired range. - 10 - • «· • t *» · * ·
    In a preferred embodiment, it is provided that the operating temperature in a heating process by means of an external heat source, in particular a solar system, is achieved. Accordingly, the photoelectrochemical cell is first preheated to operating temperature; then the external heat source is preferably decoupled from the cell. The heat input required to maintain the operating temperature occurs during operation, in particular by concentrated solar radiation.
    A first preferred embodiment variant of the invention provides that, for the decomposition of water, superheated steam having a temperature of at least 300 °, preferably more than 500 °, is supplied as starting material. At the stated operating temperatures, the chemical potential for the decomposition of the water vapor is much lower than at room temperatures when water is in the liquid state.
    A further preferred embodiment provides that the carbon dioxide decomposition as starting material carbon dioxide at a temperature of at least 600 °, preferably more than 700 °, is fed. Thus, at the second electrode, i. the cathode, which reduces carbon dioxide to carbon monoxide.
    For optimal utilization of the solar energy, it is advantageous if the heat energy of the product gas obtained at the second electrode or a gaseous by-product formed at the first electrode in a heat energy recovery circuit is used for heating the starting material. Thus, the heat energy of the product gas or any by-products is not lost, but is recovered to heat the feedstock at the desired operating temperature. The recovery of the heat energy is preferably carried out by means of heat exchangers, which are known in the prior art in various designs.
    In order to keep the operating temperature as constant as possible even under changing conditions, it is advantageous if the operating temperature is measured and regulated to a specified value. ♦ ·
    ψ · * «• · 11
    Accordingly, a measuring element is arranged, for example, at the second electrode, which measures the instantaneous operating temperature and transmits as input to a control loop, which regulates the operating temperature to the specified value. For this purpose, the control loop can be coupled to a tracking for the photo-electrochemical cell, which can influence the angle of inclination of the first electrode to the incident solar radiation. In addition, the control loop may be coupled to the external heat source to provide additional heat input into the photoelectrochemical cell when needed.
    The invention will be explained below with reference to exemplary embodiments illustrated in the drawings, to which, however, it should not be restricted.
    In detail, in the drawings:
    Fig. 1 is a schematic view of a photoelectrochemical cell formed according to a first embodiment of the invention in the manner of a panel, wherein two plate-shaped electrodes are provided, between which an ion-conducting electrolyte of a heat-resistant solid material is arranged;
    2 shows schematically the functional principle of a photovoltaic-mixing cell for hydrogen production, which according to a first embodiment variant has a 02_-ion-conducting solid oxide electrolyte;
    3 schematically shows the functional principle of a photoelectrochemical cell for hydrogen production, wherein according to a second embodiment variant an H + -ion-conducting solid oxide electrolyte is provided;
    4 shows schematically the functional principle of a photoelectrochemical cell for the reduction of carbon dioxide in carbon monoxide;
    Fig. 5 is a block diagram of a plant for hydrogen production with a photo-electrochemical cell according to Fig. 2; - 12 - 4 «* • · · * ··· #
    Fig. 6a is a cross-sectional view of a photoelectrochemical cell which is cylindrically shaped according to another embodiment of the invention; and
    Fig. 6b is a longitudinal section of the photoek-electrochemical cell shown in Fig. 6a.
    Fig. 1 shows schematically a photoelectrochemical cell 1 for solar-powered decomposition of a starting material into a product gas bound therein. The recovered product gas is in particular a gaseous energy carrier such as (molecular) hydrogen or carbon monoxide. The cell 1 has a photoelectrically active first electrode 2 which during operation is exposed to the solar radiation 3 'of the sun 3 (shown schematically in FIG. 1). The solar radiation 3 'excites in the first electrode 2, which consists of a semiconductive material, electron-hole pairs; under solar irradiation, the charge carrier density in the first electrode 2 is thus increased. The excitation of the first electrode 2 is based on the internal photoelectric effect, which is understood to mean increasing the conductivity of the electrode material by exciting electrons from the valence band into the conduction band. For this purpose, the energy of the excitation radiation must be greater than the band gap of the semiconductive material of the first electrode 2. The excited electrons are conducted via an electron conductor 4 to a second electrode 5. For closing the circuit, an ion conductor 6 is provided, which is arranged to transport ions between the first electrode 2 and the second electrode 5. In the embodiment shown in Fig. 1, the second electrode 5 is connected to a supply line 7, via which the starting material is supplied in the direction of arrow 8. The starting material is decomposed by means of the charge carriers which are present in the first electrode 2 in the form of electron-hole pairs, wherein the product gas obtained leaves the photoelectrochemical cell 1 via a discharge line 9 in the direction of arrow 10. During the decomposition of the starting material, ions are formed which are transported between the electrodes 2, 5 via the ion conductor 6. In the region of the first electrode 2, discharges 11 for a by-product are also shown schematically, which form the photo-electrochemical cell 1 in FIG. 4. In FIG.
    f I
    Arrow direction 11 'leaves. The arrangement of the supply line 1 and the discharge line 9 depends on the reactions taking place and may be different from the embodiment shown in FIG. 1, as can be seen from FIG. The reactions taking place in the photoelectrochemical cell 1 are explained in more detail below in connection with preferred embodiments; the decomposition of water into molecular hydrogen will be described with reference to FIGS. 2 and 3 and the reduction of carbon dioxide in carbon monoxide with reference to FIG. 4.
    Known cells of this type have an electrolyte solution for ion transport, which flows around the electrodes. However, the electrolytic solution has the disadvantage that photo-corrosion may occur at the irradiated electrode, with electrode material going into solution. This can lead to irreparable cell damage. Moreover, in the known cells disadvantageously only a narrow bandwidth of the solar radiation is used, namely those short-wave radiation components whose photon energy (illustrated in FIG. 1 by "hv") is greater than the band gap of the semiconducting material of the photoelectrode. The properties of the solar radiation 3 'as thermal radiation, which according to the (in Fig. 1 illustrated with)
    Stefan Boltzmann radiation law cause a heat input into the cell 1, but were neglected as an undesirable side effect.
    On the other hand, in the photoelectrochemical cell 1 shown in the drawings, there is provided as the ion conductor 6 an electrolyte made of a heat-resistant solid material disposed between the electrodes 2, 5. As a solid electrolyte, in particular a solid oxide material is provided, which is thermally stable over a wide temperature range. As a result, on the one hand, the photocorrosion of the electrode 2, which frequently occurs in the case of liquid electrolyte solutions, can be prevented. In addition, the efficiency of the photoelectrochemical cell 1 can be increased, since substantially the entire spectrum of the solar radiation 3 'contributes directly or indirectly to the decomposition of the starting material. As with conventional photoelectrochemical cells 1, with the short-wave radiation components in the photoactive material of the first electrode
    4 4 * * * * · 4 «♦ ·« 4 * I · «·! «.»:. · .. *: ι: 14 - 2 photoelectrons excited. The radiation components with a lower photoenergy than the band gap of the semiconducting material of the first electrode 2 cause a heat input into the photo-electrochemical cell 1. This also applies to the excess energy of the short-wave radiation components, i. the energy difference between the higher energy edge of the bandgap and the photon energy. The heat input by the solar radiation 3 'is converted into internal energy of the photo-electrochemical cell 1 in order to increase the operating temperature of the photo-electrochemical cell 1 to room temperature, which was avoided or was undesirable in the known cells. Due to the use of heat-resistant materials, in particular the solid electrolyte for the ion conductor 6, the photo-electrochemical cell 1 can withstand the increased operating temperature. The increase in the operating temperature on the one hand has the positive effect that the decomposition voltage required for the decomposition of the starting material into the product gas decreases. In addition, the semiconducting materials used for the photoactive first electrode 2 have a temperature-dependent band gap, which is reduced when the temperature increases. Thus, the electron yield in the photoactive first electrode 2 can be increased, so that a larger current is conducted to the second electrode 5, which increases the conversion of the starting material into the product gas. Due to the utilization of the thermal radiation properties, the cell 1 according to the invention is thus designed as a photoelectric-thermochemical cell, for which the abbreviation PETC ("Photoelectrical-Thermochemical Cell") is proposed.
    As further shown in Fig. 1, the photo-electrochemical cell 1 is formed as a flat panel 12 which is embedded in a housing 13. The electrodes 2, 5 together with the solid electrolyte arranged therebetween form a thin-layer structure, wherein the electrodes 2, 5 and the solid electrolyte are designed as large-area plates. Thus, a planar arrangement of the photo-electrochemical cell 1 is provided. At the side of the solar radiation 3 'facing side, the housing 13 has an entrance window 14 which is permeable to the incident solar radiation. For this purpose, the entrance window 14 may be made of quartz glass. Thus, a compact photo-electrochemical cell 1 is realized, which is used in the manner of a solar panel can come.
    As further schematically illustrated in FIG. 1, the electron conductor 4 may optionally have a voltage or current source 15 (denoted by Wel in FIG. 1) which controls the transport of the electrons excited in the first electrode 2 by the solar radiation 3 'to the second Electrode 5 supported. In contrast to known, different types of electrolysis apparatus, however, such an external voltage or current source 15 is not necessarily provided, since the predominant portion of the current in the photo-electrochemical cell 1 itself is generated by solar energy. The electron conductor 4 has a in the drawing schematically with "R". designated resistance to; the potential difference between the electrodes 2, 5 is indicated by " V ".
    Figs. 2 and 3 respectively show schematically the application of the photoelectrochemical cell 1 shown in Fig. 1 for the decomposition of water into molecular hydrogen and oxygen.
    Hydrogen has hitherto been used primarily in the chemical and metallurgical industries. The hydrogen is used for the preparation of intermediate compounds such as ammonia and methanol or as a chemical reducing agent. Another application is in mineral oil processing and in the production of synthetic fuels and lubricants. At present, hydrogen is predominantly produced from fossil fuels. It is expected that the demand for hydrogen will increase. On the one hand, increased demand from the chemical industry, for example for fertilizer production, can be expected. In addition, hydrogen is increasingly gaining importance as fuel for power and heat generation by means of fuel cells. Hydrogen can thus help to reduce the use of fossil fuels. The production of hydrogen as fuel and fuel, however, only makes sense energetically and ecologically if predominantly regenerative energies can be used for this purpose.
    Thus, there is a great need to use regenerative energies efficiently for hydrogen production, which is comparable to that in the US Pat. No. 4,200,099. ♦ · ··· Ο - 16 - 'i ί «
    Fig. 2 and 3 shown photoelectrochemical cell 1 can be achieved.
    Fig. 2 shows a first embodiment of the photoelectrochemical water separation, which is based on a 02'-ion-conducting Feststof foxide material as the electrolyte.
    As the photoactive material for the first electrode 2, a heat-resistant metal oxide, suitably TiO 2 or Cu 2 O, having a porous structure and semiconductive properties is used. The first electrode 2 is exposed on one side of the solar radiation 3 '. Arranged on the side of the first electrode 2 facing away from the sun 3 is the ion conductor 6, which is formed by a high-temperature resistant solid electrolyte, in particular a solid oxide electrolyte (eg yttrium-doped zirconia, in short: YSZ, "yttria-stabilized zirconia") is. Upon irradiation of the first electrode 2, two electron-electron-pair pairs are generated in the semiconducting material of the first electrode (equation 1). 2hv - 2e + 2Υΐ Eq. 1
    The electrons e " move in the direction of the irradiated side of the first electrode 2. The holes h + migrate against the flow of electrons to the interface with the ion conductor 6. The electrons e- are connected via an external circuit, i. via the electron conductor 4, to the opposite electrode 5, which forms the cathode. The electrodes 2, 5 include the solid oxide electrolyte as a thin membrane. Due to the flow of electrons, the ion conductor 6 facing side of the semiconducting material of the first electrode 2 to the anode. In order to keep the electron-hole recombination in the first electrode 2 low, the electron flow generated via the electron conductor 4 is supported by the external voltage source 15, which amplifies the photoelectrically generated electric field. By means of the voltage source 15, the generated electrons e- "sucked", whereby the electron-hole recombination is substantially reduced.
    At the cathode forming the second electrode 5 is superheated • · ·
    The water vapor H20 (t, which forms the starting material for the hydrogen production, is supplied at a temperature of more than 300 ° C., in particular more than 500 ° C. At the second electrode 5, electrons e- cause water vapor H20 (q!) to be reduced to molecular hydrogen H2 and oxygen ions O2 ^ (equation 2). H20 (gi + 2e - H2lg) + Ο2 'Eq
    The '02' ions pass through the solid electrolyte of the membranous ionic conductor 6 to the interface to the anode of the semiconducting first electrode 2. There, the O 2 'ions recombine with the holes h + migrating from the other side to molecular oxygen O 2 (Equation 3). + 2h + - * i 02 (g) Eq. 3
    By means of pore diffusion, the molecular oxygen O 2 passes through the semiconducting material of the first electrode 2, exits on the irradiated side and is discharged as a by-product. The overall reaction (equation 4) of the photoelectro-thermochemical water decomposition is the sum of the individual reaction steps from equations Eq. 1 - Eq. 3. 2hv + H20fg) ~ * H2 (g) + i 02 (g) Eq. 4
    The process for decomposing water proceeds at operating temperatures of more than 300 ° C, preferably between 500 ° and 900 ° C, wherein the increased operating temperature is at least partially generated by the heat input of the solar radiation 3 '. At temperatures of 500-900 ° C. or 773.15-1173.15 K, the thermodynamically required voltage potential (decomposition voltage) of 1.23 V at room temperature (298.15 K) and an ambient pressure of 1 bar is reduced to about 1 - 0.9 V. In order to increase the heat input into the photo-electrochemical cell 1, preferably concentrated solar radiation 3 '' is used, as further explained in connection with FIG.
    FIG. 3 shows an alternative embodiment of the photoelectrochemical decomposition of water into molecular hydrogen and molecular oxygen which provides an H + ion (proton) conductive solid oxide material as an electrolyte. For transporting the H + ions, a lanthanum mixed oxide is particularly suitable.
    The processes taking place in the photoelectrochemical cell 1 according to FIG. 3 are characterized by the equations 5-9 given below.
    According to Fig. 2, the solar generation of electron-hole pairs (equation 5) takes place at the first electrode 2: 2hv ^ 2e ~ + 2h * Eq. 5
    In this embodiment, the water vapor H20 (g) is supplied to the first electrode 2, which is suitably made of Cu20. The photoelectrically generated holes h + cause in the first electrode 2 an anodic oxidation of the water vapor H20 (g), wherein molecular oxygen OZ and hydrogen ions H +, which migrate in the direction of the boundary layer to the ion conductor 6, arise. (Equation 6): H 2 O 3 + 2h * - 3 O 2 (g > + 2H * Eq
    The oxygen O 2 is derived as a by-product of the hydrogen recovery. The hydrogen ions H + reach via the ion conductor 6 to the second electrode 5, i. to the cathode, which is suitably made of platinum. At the second electrode 5, the H + ions combine with the supplied electrons e- to form molecular hydrogen H2, which is derived as product gas (equation 7): 2H * + 2e ~ H2 (g, equation 7
    The total photoelectrochemical reaction can therefore be read as follows (equation 8): 2hv + H 2 O fg) - * H 2 (g) + 3 O 2 (gf equation 8
    As can also be seen schematically from FIG. 2 and FIG. 3, between the solid electrolyte and the first electrode 2, there is always a difference between the solid electrolyte and the first electrode 2 * * * *·· * * * * *.
    φ ···· · * ♦ · Weil a catalyst layer 16 is arranged. The material for this catalyst layer 16 depends on the ions which are transported via the electrolyte. For promoting the hydrogen evolution in the case of H + ion conduction, a thin film of platinum may suitably be provided; the oxygen evolution in the case of the 02-ion line can be catalyzed with a catalyst layer 16 of ruthenium oxide (RuO 2).
    Fig. 4 shows schematically a photo-electrochemical cell 1, which is arranged according to a further embodiment of the invention for the reduction of carbon dioxide CO 2 in carbon monoxide CO. With regard to the materials for the ion conductor 6, the catalyst layer 16 and the electrodes 2, 5, reference may be made to the photoelectrochemical cell 1 explained in connection with FIG. 3 with 02'-ion conductive solid oxide material as the electrolyte.
    Eq. 9 shows the generation vs> n electron-hole pairs taking place at the first electrode 2:
    Eq. 9 2hv - * 2e ~ + 2h
    The carbon dioxide C02 is supplied to the second electrode 5 to react with the supplied electrons e 'to carbon monoxide CO and oxygen ions 02_ (equation 10):
    Eq. 10 C02 (g) + 2e - CO (g) + O2 '
    The O 2 ions migrate through the ion conductor 6 to recombine with the photogenerated holes h * to form molecular oxygen (equation 11):
    Eq. 11 Ο2 '+ 2h + 02 <g)
    Thus, the overall photoelectrochemical reaction is:
    Eq. 12 2h V + CO 2 (g) - * CO (g) + 3 02 (g)
    The conversion of the carbon dioxide takes place at a temperature of at least 600 ° Celsius, preferably more than 700 ° Celsius, at a temperature of -20- * Μ * I * * · * ···········, in order to explain the advantages of the reduced band gap of the invention explained with reference to the water decomposition semiconducting material of the first electrode 2 and the lower decomposition voltage to use.
    Fig. 5 shows in a schematic block diagram a hydrogen production arrangement 17 with a photoelectrochemical cell 1 according to Fig. 2; Of course, the assembly 17 may alternatively be equipped with the electrochemical cell 1 shown in Fig. 3 or Fig. 4 to allow alternative embodiment of water separation (as shown in Fig. 3) and reduction of carbon dioxide (as shown in Fig. 4).
    As shown in Fig. 5, the photoelectrochemical cell 1 is covered with an insulating body 18 which protects the photo-electrochemical cell 1 from heat radiation to maintain the desired elevated operating temperature (TB in Fig. 5). The insulating body 18 has an open recess 19 in the direction of the incident solar radiation 3 ', which accommodates the photoelectrochemical cell 1. The solar radiation 3 'is coupled via the entrance window 14 into the photoelectrochemical cell 1.
    In order to increase the heat input into the photo-electrochemical cell 1, a device 19 for focusing the incident solar radiation 3 'is arranged between the radiation source 3 and the photo-electrochemical cell 1. The intensity of the concentrated solar radiation 3 "impinging on the first electrode 2 is preferably increased by means of the device 19 by a factor of at least 30, in particular by a factor of at least 50, from the intensity of the incident solar radiation 3 '. The focusing of the solar radiation can be achieved with well-known in the prior art focusing devices; In the case of the panel 12 with a substantially planar electrode 2 shown in FIGS. 1 and 5, it is expedient to provide a surface-focusing device 19, for example a heliostat known from solar tower power plants. The heat input by the concentrated solar radiation 3 '* makes it possible to increase the operating temperature TB of the cell 1 to a level significantly higher than room temperature
    «. As described above, the increased operating temperature TB is advantageous in view of the efficiency of the processes occurring in the photovoltaic cell 1. FIG. 5 also schematically shows an optical unit 21, which is set up to image the solar radiation 3 "concentrated by means 19 in a suitable manner onto the photoactive first electrode 2. From Fig. 5 is further schematically the external current or voltage source 15 can be seen, which is optionally connected to the electron conductor 4, to support the flow of current between the electrodes 2, 5.
    The arrangement 17 is set up to automatically maintain the increased operating temperature TB via the coupled-in solar radiation 3 ', 31'. In order to reach the operating temperature TB in a heating process, an external heat source 22 is provided, which is set up to transmit a heat flow Qi to the photoelectrochemical cell 1. The external heat source 22 can also serve to buffer fluctuations in the solar radiation 3 'occurring during operation. For this purpose, the heat source 22 is configured to transmit a variable heat flow Qi to the photo-electrochemical cell 1 or to receive a variable heat flow Q2 from the photo-electrochemical cell 1 as needed. The heat source 22 is supplied for example by a solar system; Of course, a heat source 22 based on electrical or chemical energy is conceivable.
    The assembly 17 has a feed 23 for the starting material, i. Water H20, which is passed to a superheater 24, the superheated steam H20 <g, preferably with a temperature of at least 300 ° generated. The superheated steam H20 (g) is supplied to the second electrode 5 of the photoelectrochemical cell 1, in which the processes described in connection with FIG. 2 for decomposing the water vapor H20 (g) into molecular oxygen O2 and molecular hydrogen H2 proceed.
    At the second electrode 5 a mixture of molecular hydrogen H2 and water vapor H20 [g), which contains a certain amount of heat Q, is formed. The mixture of molecular hydrogen H2 and water vapor H20 (g) is fed to a separator 25 which contains the
    Product gas H2 from the remaining water vapor H20ig) separates. The separator 25 is further configured as a heat energy recovery means to transfer a heat flow Q3 of the H2 / H20 (g, gas mixture to the superheater 24. Thus, the heat energy of the product gas (or the remaining raw material) in a heat energy recovery circuit is used For this purpose, a heat exchanger may be used, for which various designs are known in the prior art The separator 25 is connected to a reservoir 26, which receives the cooled product gas H2 The cooled water H20 is supplied to a separate reservoir 27 The water decomposition in the photoelectrochemical cell 1 is generated at the first electrode 2 (according to the embodiment shown in FIG. 3 at the second electrode 5) ) molecular oxygen 02, the supra the discharge 11 is passed to a further heat energy recovery device 29, which transfers a heat flow Q * to the superheater 24 in order to use the heat energy of the by-product to heat the starting material. The cooled by-product 02 is supplied to a reservoir 30.
    In order to compensate for fluctuations in the operating temperature TB, a control circuit 31 is provided, which regulates the operating temperature TB to a predetermined value. The control circuit 31 has a measuring element 32 for measuring the operating temperature TB, which may be arranged, for example, on the second electrode 5. The measuring element 32 supplies the operating temperature TB to a controller 33, which determines a control deviation to a specified value for the operating temperature TB. To adjust the operating temperature TB, the controller 33 is connected to the external heat source 22 in order to increase or decrease the heat input into the photo-electrochemical cell 1 in accordance with the control deviation. Alternatively or additionally, the controller 33 may be connected to a track 34, which may influence the angle of inclination between the solar radiation 3 '(or 3' ') and the photoelectrochemical cell 1, especially the first electrode 2.
    FIGS. 6a and 6b show an alternative embodiment of the invention for panel-like construction of the photoelectrochemical cell 1 according to FIGS. 1, 5, which provides a rod-shaped or cylindrical construction.
    According to FIGS. 6a, 6b, the entrance window 14, the first electrode 2, the electrolyte 6 and the second electrode 5, from outside to inside, are formed as adjoining hollow-cylindrical layers. Alternatively, a structure with differently curved, for example, spherically curved layers would be conceivable. In addition, a half-shell-shaped insulating body 18 can be seen, which surrounds the side facing away from the radiation source 3 half of the photo-electrochemical cell 1.
    In Fig. 6b is further schematically illustrated the supply of the starting material in the direction of arrow 7 and the discharge of the product gas in the direction of arrow 10 at the second electrode 5. The resulting in the decomposition of the starting material gaseous by-product is discharged via an outlet 11 in the direction of arrow 11 '.
    In the embodiment of the photoelectrochemical cell 1 shown in FIGS. 6a, 6b, a line-focusing device 19 for bundling the incident solar radiation 3 'can be provided, which can be formed, for example, by a Paraboir indoor or Fresnel concentrator.
    The embodiment of the photoelectrochemical cell 1 shown in FIGS. 6a, 6b can be operated in accordance with the embodiments explained with reference to FIGS. 1 to 5, so that reference is made to the above explanations for this purpose - in particular also with regard to the materials used, preferred operating conditions and temperature ranges can.
    权利要求:
    Claims (19)
    [1]
    - 24 - Claims: 1. Photoelectrochemical cell (1) for solar-powered decomposition of a starting material, in particular water or carbon dioxide, into a product gas bound therein, in particular hydrogen or carbon monoxide, with a supply line (7) for the starting material and a discharge (9) for the product gas obtained, having a first electrode (2) of a photoelectrically active material and a second electrode (5) exposed to the action of solar radiation (3 ', 3' '), the electrodes (2, 5) being in a closed circuit connected by an electron conductor (4) for transporting electrons excited by the solar radiation (3 ', 3' ') in the first electrode (2) and an ionic conductor (6) for transporting ions formed during the decomposition of the starting material characterized in that as ion conductor (6) between the electrodes (2, 5) arranged electrolyte is provided from a heat-resistant solid material.
    [2]
    2. Photoelectrochemical cell (1) according to claim 1, characterized in that the electrolyte consists of a solid oxide mate rial, in particular zirconium dioxide (ZrO 2) or a lanthanum mixed oxide, preferably Lanthanzirkonat {LaZr03) or Lanthancer-nat (LaCe03) ,
    [3]
    3. Photoelectrochemical cell (1) according to claim 2, characterized in that the solid oxide material is doped with a rare earth metal, in particular with yttrium.
    [4]
    4. Photoelectrochemical cell (1) according to any one of claims 1 to 3, characterized in that the first electrode as an anode of a transition metal oxide <MeOx), preferably Fe203, CoO, Cu20, NiO, Sn02 / Ti02, W03 or ZnO made is.
    [5]
    5. The photoelectrochemical cell (1) according to claim 1, characterized in that the second electrode (5) is a cathode made of a catalytically active material, in particular RuO 2, LaSrMnO 3, Pt, a metal-ceramic mixture, preferably nickel. YSZ, or Ni is made. ft

    • ft • ft • ft • ft • ft • ft • ft ft • ft • ft • ft • ft


    [6]
    6. The photoelectrochemical cell (1) according to any one of claims 1 to 5, characterized in that the electron conductor (4) a voltage or current source {15) to support the transport of the solar radiation (3 ', 3' ') excited Having electrons.
    [7]
    7. Photoelectrochemical cell (1) according to one of claims 1 to 6, characterized in that one of the electrodes (2, 5) with a discharge (11) for a resulting by the decomposition of the starting material gaseous by-product, in particular oxygen, is connected.
    [8]
    8. Photoelectrochemical cell (1) according to one of claims 1 to 7, characterized in that between one of the electrodes (2, 5) and the electrolyte, a catalyst layer (16), in particular of Pt, RuO 2, Ni, Ni-YSZ, or LaSrMn03, is arranged.
    [9]
    9. Photoelectrochemical cell (1) according to one of claims 1 to 8, characterized in that the first electrode (2) is associated with a device (19) for focusing the incident solar radiation (3 '), which is adapted to the intensity of a on the first electrode (2) bundled solar radiation (3 * ') to increase at least 30 times, preferably at least 50 times, with respect to the incident solar radiation (3').
    [10]
    10. The photoelectrochemical cell (1) according to any one of claims 1 to 9, characterized in that the electrodes (2, 5) and the electrolyte for obtaining a panel (12) are accommodated in a flat housing (13), one of the first Electrode (2) covering the light-transmitting entrance window (14), in particular a glass pane having.
    [11]
    11. Photoelectrochemical cell (1) according to claim 10, characterized in that the housing (13) by an insulating body (18) is sheathed, which has a the entrance window (14) corresponding recess.
    [12]
    12. Method of Solar-Driven Decomposition of a Source »« · · · · · «Μ ·····················································································. Substance, in particular water or carbon dioxide, in a product gas bound therein, in particular hydrogen or carbon monoxide, wherein in a photoelectrically active first electrode (2) by means of solar radiation (3 ', 3' ') charge carriers in Form of electron-hole pairs are excited, wherein the excited electrons are conducted to a second electrode (5) and one of the electrodes (2, 5), the starting material is fed, which is decomposed by the excited charge carriers, wherein ions are generated, which are transported in a closed circuit to the respective other electrode (2, 5), wherein the recovered product gas is derived, characterized in that the ion transport between the electrodes (2, 5) via an electrolyte of a solid material, in particular a solid oxide material.
    [13]
    13. The method according to claim 12, characterized in that the excitation of the first electrode (2), the ion transport and the decomposition of the starting material at an operating temperature (TB) of more than 300 ° Celsius, preferably more than 500 ° Celsius, takes place.
    [14]
    14. The method according to claim 12 or 13, characterized in that the first electrode (2) with concentrated solar radiation (3 '') is irradiated, the intensity of which is at least 30-fold, preferably at least 50-fold, opposite the intensity of the incident solar radiation (3 ') is increased.
    [15]
    15. The method according to any one of claims 12 to 14, characterized in that the operating temperature (TB) in a heating process by means of an external heat source (22), in particular a. Solar system, is achieved.
    [16]
    16. The method according to any one of claims 12 to 15, characterized in that for the decomposition of water as the starting material superheated steam at a temperature of at least 300 ° Celsius, preferably more than 500 ° C, is supplied.
    [17]
    17. The method according to any one of claims 12 to 15, characterized in that the carbon dioxide decomposition as a starting material carbon dioxide at a temperature of at least 600 ° C, preferably more than 700 ° C, is fed.
    [18]
    18. The method according to any one of claims 12 to 17, characterized in that the heat energy of the product at the second electrode (5} product gas or at the first electrode (2) resulting gaseous by-product used in a heat energy recovery circuit for heating the starting material becomes.
    [19]
    19. The method according to any one of claims 13 to 18, characterized in that the operating temperature (TB) is measured and regulated to a predetermined value.
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    同族专利:
    公开号 | 公开日
    IL225533A|2017-10-31|
    CN103370447A|2013-10-23|
    US20150167179A1|2015-06-18|
    IL225533D0|2013-06-27|
    AU2011313800A1|2013-05-02|
    AT510156B1|2012-02-15|
    MX2013003739A|2013-12-06|
    ES2558004T3|2016-02-01|
    EP2625315A1|2013-08-14|
    WO2012045104A1|2012-04-12|
    AU2011313800B2|2016-01-28|
    EP2625315B1|2015-09-30|
    MX338890B|2016-05-04|
    CN103370447B|2017-02-08|
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    法律状态:
    2014-09-15| PC| Change of the owner|Owner name: NOVAPECC GMBH, AT Effective date: 20140716 |
    优先权:
    申请号 | 申请日 | 专利标题
    AT0165510A|AT510156B1|2010-10-04|2010-10-04|PHOTOELECTROCHEMICAL CELL|AT0165510A| AT510156B1|2010-10-04|2010-10-04|PHOTOELECTROCHEMICAL CELL|
    CN201180056409.XA| CN103370447B|2010-10-04|2011-10-03|Photoelectrochemical cell and method for the solar-driven decomposition of a starting material|
    AU2011313800A| AU2011313800B2|2010-10-04|2011-10-03|Photoelectrochemical cell and method for the solar-driven decomposition of a starting material|
    PCT/AT2011/000408| WO2012045104A1|2010-10-04|2011-10-03|Photoelectrochemical cell and method for the solar-driven decomposition of a starting material|
    US13/877,686| US20150167179A1|2010-10-04|2011-10-03|Photoelectrochemical cell and method for the solar-driven decomposition of a starting material|
    ES11779080.8T| ES2558004T3|2010-10-04|2011-10-03|Photoelectrochemical cell and procedure to decompose a starting material by solar energy|
    MX2013003739A| MX338890B|2010-10-04|2011-10-03|Photoelectrochemical cell and method for the solar-driven decomposition of a starting material.|
    EP11779080.8A| EP2625315B1|2010-10-04|2011-10-03|Photoelectrochemical cell and method for the solar-driven decomposition of a starting material|
    IL225533A| IL225533A|2010-10-04|2013-04-02|Photoelectrochemical cell and method for the solar- driven decomposition of a starting material|
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